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The selective synthesis of 2,6-naphthalenedicarboxylic acid from 2-naphthalenecarboxylic acid with carbon tetrachloride, copper powder, and aqueous alkali was achieved by using of β-cyclodextrin (β-CyD) as a catalyst at 60°C under nitrogen, producing 2,6-naphthalenedicarboxylic acid in 67 mol% yield with 84% selectivity. The one-pot preparation of 2,6-naphthalenedicarboxylic acid from naphthalene was attained at 84°C by using of β-CyD, producing 2,6-naphthalenedicarboxylic acid in 65 mol% yield with 79% selectivity. When α-CyD or γ-CyD was used instead of β-CyD on the carboxylation of 2-naphthalenecarboxylic acid and naphthalene, respectively, the reaction hardly proceeded. The conformation of β-CyD–2-naphthalenecarboxylate inclusion complex in aqueous alkaline solution was determined by the nuclear magnetic resonance spectroscopy using 1 H homonuclear Overhauser enhancement on the rotating frame. The 2-naphthalenecarboxylate anion was axially included in the cavity of β-CyD with an orientation which directed the 5-, 6-, and 7-positions of 2-naphthalenecarboxylate anion to the secondary hydroxyl side of β-CyD. It was concluded that the high selectivity of the carboxylation of 2-naphthalenecarboxylic acid was ascribed to the conformation of the β-CyD–2-naphthalenecarboxylate inclusion complex. The selective carboxylation of naphthalene was attributed to the formations of the β-CyD–naphthalene and β-CyD–2-naphthalenecarboxylate inclusion complexes.

ポリ (N-ビニル-2-ピロリドン) (PVP) に保護されたパラジウムナノ粒子 (PVP-Pdナノ粒子) をメタノール分散液中からトリメチルアンモニウム基を有するポリスチレンゲル (PSt-TA) に吸着させることを試みた. PVP-Pdナノ粒子は, ゲル型のPSt-TAに吸着されず, 多孔型のPSt-TA (PSt-HPA) (平均細孔径140nm) に吸着された. PVPの平均分子量 (Mw: 6000, 25000, 175000, および574000) が増加するにつれ, PVP-Pdナノ粒子のPSt-HPAへの吸着量は減少した. 超遠心法によりPVPの吸着層を含めたPVP-Pdナノ粒子の粒径を測定した結果, Mwが増加するにつれ, この粒径は増加した. PSt-HPAに吸着されたPVP-Pdナノ粒子は, 1, 3-シクロオクタジエンの水素化反応の触媒として. 10回以上の繰り返し使用においても最初の活性および選択性を保持した.

炭素繊維の繊維束内に, ピッチコークス, メソフェーズピッチ, および鱗片状コークスなどのマトリックス粉を包含させ, ポリプロピレンで被覆することによりプリフォームドヤーンを作製した. このプリフォームドヤーンを金属製の芯棒にらせん状に巻いてホットプレス成形することにより, 炭素繊維強化炭素製コイルスプリングの作製を行った. 炭素繊維に紡績糸を用いたプリフォームドヤーンを使用して作製したスプリングは, フィラメント糸を用いたものと比較して高いばね定数を示した. 紡績糸の体積含有率を35～75 vol%で変化させると, ばね定数は含有率が60 vol%のときに最も高い値を示した. マトリックス組成を変化させると, メソフェーズピッチが60 wt%, ピッチコークスが34.6 wt%, 燐片状コークスが6.4 wt%のときばね定数は最も高い値を示した. 一方, 繊維配向が二次元の炭素繊維強化炭素製ブロックから削り出して作製したコイルスプリングは, 非常に低いばね定数しか示さなかった.

The selective synthesis of terephthalic acid from benzoic acid with carbon tetrachloride, copper powder, and aqueous alkali was achieved by the use of β-cyclodextrin (β-CyD) as a mediator at 60°C under nitrogen of atmospheric pressure, producing terephthalic acid in 74 mol% yield with 100% selectivity. When α-CyD or γ-CyD was used instead of β-CyD, the reaction hardly proceeded. The addition of p-benzoquinone to the reaction mixture decreased the yield of terephthalic acid remarkably. An oxygen atmosphere also suppressed the reaction appreciably. Thus, the active species formed from carbon tetrachloride and copper powder in the reaction mixture is proposed to be trichloromethyl radical. The conformations of CyD-benzoate inclusion complexes in aqueous alkaline solution were determined by the nuclear magnetic resonance spectroscopy using 1H homonuclear Overhauser enhancement on the rotating frame. The benzoate anion was axially included in the cavity of β-CyD with orientation such that the carboxylate group was at the primary hydroxyl side of β-CyD. The essential factor of the carboxylation by the use of β-CyD was the inclusion complex formation of β-CyD with benzoate anion and β-CyD with carbon tetrachloride in the reaction mixture. The very high selectivity was ascribed to the conformation of the β-CyD-benzoate inclusion complex.

The conformations of β-cyclodextrin (β-CyD)-benzoate and β-CyD-biphenylcarboxylate inclusion complexes have been determined by 1 H ROESY NMR spectrometry.

Stable dispersions of colloidal gold in n-hexane and cyclohexane have been prepared by transfer of colloidal gold particles from an aqueous phase to a n-hexane phase and to a cyclohexane phase, respectively. The phase transfer of gold particles occurred on addition of magnesium chloride to the emulsion of hexane in the aqueous suspension of gold with sodium oleate. The size distributions of the gold particles in the resulting colloidal gold in hexane suspensions were almost the same as that (mean diameter 14 nm, standard deviation 1.5 nm) of the original aqueous suspension of gold. The critical phase-transfer concentrations of various salts were determined. The phase-transfer powers of cations were larger than those of unions. Those of divalent and trivalent cations were exceedingly larger than that of the monovalent cation.

Four anionic surfactants having two polyfluoroalkyl chains in a molecule, sodium salt of bis(1H,1H,2H,2H-heptadecafluorodecyl) 2-sulfosuccinate, CF3(CF2)7(CH2)2OCOCH2CH(SO3Na)COO(CH2)2(CF2)7CF3, sodium salt of bis(1H,1H,9H-hexadecafruorononyl) 2-sulfosuccinate, H(CF2)8CH2OCOCH2CH(SO3Na)COOCH2(CF2)8H, sodium salt of bis(1H,1H,7H-dodecafluoroheptyl) 2-sulfosuccinate, H(CF2)6CH2OCOCH2CH(SO3Na)COOCH2(CF2)6H and sodium salt of bis(1H,1H,5H-octafluoropentyl) 2-sulfosuccinate, H(CF2)4CH2OCOCH2CH(SO3Na)COOCH2(CF2)4H, were prepared from maleic anhydride, the corresponding alcohols having a polyfluoroalkyl chain and sodium hydrogensulfite. The flocculation and redispersion abilities of these surfactants against dispersed magnetite particles in water have been examined in comparison with other four anionic surfactants having a single polyfluoroalkyl chain in a molecule; sodium pentadecafluorooctanoate, CF3(CF2)6COONa, sodium 9H-hexadecafluorononanoate, H(CF2)8COONa, sodium 7H-dodecafluoroheptanoate, H(CF2)6COONa, an...

Titanium butoxide tris(5H-octafluoropentanoate), Ti(OnC4H9)[OCO(CF2)4H]3, titanium butoxide tris(7H-undecafluoroheptanoate), Ti(OnC4H9)[OCO(CF2)6H]3, titanium butoxide tris(9H-hexadecafluorononanoate), Ti(OnC4H9)[OCO(CF2)8H]3, and titanium butoxide tris(perfluorooctanoate), Ti(OnC4H9)[OCO(CF2)6CF3]3, were prepared by the reaction of titanium butoxide trichloride with sodium fluoro-substituted acylates in 1,1,2-trichloro-1,2,2-trifluoroethane. These compounds were characterized on the basis of elemental analysis as well as their IR, 1H NMR, 13C NMR, and 19F NMR spectra. In the compounds produced, a Ti–OCO bond was stable in water, although a Ti–OR bond was only moderately stable in water. A surface modification against calcium carbonate was attempted by using these products. From measurements of the contact angles θ(°) of water and toluene against a modified calcium carbonate surface, titanium butoxide tris(perfluorooctanoate) was found to be an effective substance for a new-type coupling agent, which incr...

Colloidal copper dispersions are prepared by reducing copper(II) ions in water with sodium tetrahydroborate or hydrazine in the presence of various protective polymers. The polymers are poly(N-vinyl-2-pyrrolidone), poly(vinyl alcohol), poly(methyl vinyl ether), poly(potassium vinyl sulfate), dextrin, amylopectin, methylamylopectin, methylcellulose, ethylcellulose, and (2-hydroxyethyl)cellulose. The dispersions are black, reddish dark brown, or reddish brown homogeneous solutions, and are stable under nitrogen at room temperature for more than three months. Electron diffraction experiments indicate that copper atoms in the colloidal particles are arranged in an ordered way, which is almost identical with that in a crystal of bulk copper metal. At the charged molar ratio 40 of the monomeric residue of the protective polymer to copper(II) ion, the average diameters of the copper particles, prepared by use of sodium tetrahydroborate, range from 50 to 150 A, depending on the polymer used. With the use of poly(...

A polymer–palladium complex prepared from palladium(II) chloride and styrene-divinylbenzene copolymer with iminodiacetic acid groups is found to catalyze the selective hydrogenation of conjugated diolefins to monoolefins at 30°C under an atmospheric hydrogen pressure.

A polymer–rhodium complex prepared from rhodium(III) chloride and styrene-divinylbenzene copolymer with iminodiacetic acid groups is found to catalyze the heterogeneous hydrogenation of alkenes in polar solvents at 30°C under an atmospheric hydrogen pressure. The polymer complex hydrogenates selectively the ethylenic double bonds in the alkenes with carbonyl and aromatic groups. The rates of hydrogenation of alkenes by the polymer complex are found to be markedly affected by the steric hindrance of the substrates.

With the use of cyclodextrins as catalysts, 4-hydroxybenzaldehydes, 4-hydroxybenzoic acids, 4-dichloromethyl-2, 5-cyclohexadienones, and indole-3-aldehyde are synthesized in virtually 100 % selectivities and in high yields. 4-Allyl-2, 5-cyclohexadienone is obtained also in 100 % selectivity using a modified cyclodextrin, in which all the primary hydroxyl groups are replaced by N-methyl-formamido groups. In addition, one-pot syntheses are successfully carried out with cyclodextrin as catalyst, yielding chalcones and β-nitrostyrenes in 100 % selectivity and in high yields. In the absence of cyclodextrins, however, both the yields and the selectivities for the desired products in all the reactions are quite low. The selective catalyses by cyclodextrins involve, a) regulation of mutual orientation of reactants, b) regulation of molecular size of intermediates and products, c) protection of unstable intermediates and products, and/or d) solubilization of reactants with poor solubilities. The mechanisms of selective catalyses are clarified using the conformations of the molecular complexes, formed from cyclodextrins and reactants in the reaction mixtures, which are determined by 1H-and 13C-NMR spectroscopy. Furthermore, 4-hydroxybenzoic acid and 4-hydroxybenzaldehyde are synthesized in almost 100 % selectivity using cyclodextrins, immobilized with epichlorohydrin as crosslinking agent, as catalysts. The immobilized catalysts are easily separated from the reaction mixtures, and are successfully used many times without measurable decrease in catalytic activities.

The photochemical conversion of N-acetyldiphenylmethyleneamine (I) in toluene to produce an addition product N-(1,1,2-triphenylethyl)acetamide and a hydrogenation product N-(diphenylmethyl)acetamide has been found to increase remarkably by displacement of para-hydrogen of toluene with a halogen (chlorine or bromine). A number of halogenated solvents, especially brominated solvents such as dibromomethane and bromobenzene, also promoted the photoreaction of the imine I with toluene. The extent of the promotion depends on the kind of a halogen atom of the solvent molecule. The reaction rate was accelerated with the number of halogen atoms of the solvent molecule. The conversion rate increased very remarkably when the concentration of bromobenzene increased from 0 to 1 mol/l. The reaction via chemical sensitization by benzophenone, a contaminant in imine I, was shown to be insensitive to the heavy atom solvent. The heavy atom effect can be attributed to an increase in the rate of intersystem crossing from the...

Carbon monoxide absorbents composed of linear polystyrene (PSt), aluminium halide, copper(I) halide, and toluene are prepared. The toluene solutions of polystyrene–protected aluminium copper(I) chloride (PSt–AlCuCl4) rapidly absorb CO at 20 °C under 1 atm (initial partial pressure of CO: 0.90 atm) and the equilibrium molar ratio of absorbed CO to the charged CuCl is 0.78. On the elevation of the temperature from 20 °C to 82 °C under 1 atm, the absorbed CO is released completely. The absorption-release cycles are repeated many times without measurable decrease in the absorbing capacity. The CO absorbing capacities of toluene solutions composed of aluminium halides, copper(I) halides, and polystyrene decrease as follows: AlCl3–CuCl system>AlBr3–CuBr system>>All3–CuI system=0. The CO absorbing activity of the toluene solution of PSt–AlCuCl4 remains virtually unchanged on the contact of the solution with nitrogen gas containing 10 mol% water to the charged CuCl (water content: 9000 ppm), when the molar ratio ...

A new dry-type adsorbent was prepared by washing the chelate resin beads holding iron(II) with a hydrophilic organic solvent, followed by vacuum drying. It adsorbed more than 99% of nitrogen oxide from 6 dm3 of nitrogen gas containing 980 ppm nitrogen oxide in 25 min. The nitrogen oxide adsorbed on the adsorbent was able to be desorbed by raising temperature up to 100 °C under vacuum.

Application of ultrafine metal particles, 10-1000 A in diameter, to organic syntheses are reviewed as reagents and catalysts. Ultrafine magnesium particles are effectively reactive to organic compounds with rather poor reactivities such as fluorobenzenes and bromobenzenes, yielding the Grignard reagents. Ultrafine zinc particles also react with less reactive bromobenzenes under mild conditions. Ultrafine particles of palladium, platinum, rhodium, ruthenium, copper, and others show high catalytic activity and selectivity in various organic syntheses. The selective catalytic reactions involve1) hydrogenation of C-C double bonds, nitro groups, and aromatic rings, 2) hydrogenation of dienes to the corresponding monoenes, 3) hydrogenolysis of cystine to cysteine, 4) hydration of acrylonitrile to acrylamide, and 5) hydration of C-C double bond, followed by dehydrogenation of the resulting alcohol. The features of ultrafine metal particles used in organic syntheses are discussed.

Homogeneous hydrations of unsaturated nitriles such as acrylonitrile, methacrylonitrile, and crotononitrile to the corresponding unsaturated amides have been carried out in water at 80°C by use of colloidal copper dispersions as catalysts. The dispersions are prepared by reduction of copper(II) sulfate, copper(II) chloride, and copper(II) acetate with sodium tetrahydroborate in the presence of various polymers. The dispersions with poly(N-vinyl-2-pyrrolidone), poly(vinyl alcohol), methylamylopectin, methylcellulose, ethylcellulose, and (2-hydroxyethyl)cellulose exhibit much larger catalytic activities than the copper precipitates prepared by reduction of the copper salts with sodium tetrahydroborate in the absence of the polymers. For all the catalytic reactions with the colloidal dispersions, selectivity for the unsaturated amides is 100% and formation of any by-products is not detected at all. Electron microscopy shows that no significant structural change occurs in the dispersions during the catalytic ...

Chlorocarbonylbis(triphenylphosphine)rhodium was obtained by the reaction of tris(triphenylphosphine)chlororhodium with carbon dioxide and hydrogen. Use of a polar aprotic solvent was effective for the reaction. This reaction indicates carbon dioxide is reduced by molecular hydrogen on a rhodium complex and fixed in the form of a carbonyl complex.

Tetrakis(1H,1H-perfluoroethyl) titanate, Ti(OCH2CF3)4, tetrakis(1H,1H-perfluoropropyl) titanate, Ti(OCH2CF2CF3)4, tetrakis(2,2,2-trifluoro-1-methylethyl) titanate, Ti[OCH(CH3)CF3]4, tetrakis(2,2,2-trifluoro-1,1-dimethylethyl) titanate, Ti[OC(CH3)2CF3]4, tetrakis((1H,1H,3H-perfluoropropyl) titanate, Ti(OCH2CF2CF2H)4, tetrakis(1H,1H,5H-perfluoropentyl) titanate, Ti[OCH2(CF2CF2)2H]4, tetrakis(1H,1H,7H-perfluoroheptyl) titanate, Ti[OCH2(CF2CF2)3H]4, and tetrakis(1H,1H,9H-perfluorononyl) titanate, Ti[OCH2(CF2CF2)4H]4, were prepared by the reaction of titanium tetrachloride with fluoro-substituted alcohols in the presence of ammonia. Tetrakis(pentafluorophenyl) titanate, Ti(OC6F5)4 was synthesized by the ester interchange reaction of tetraisopropyl titanate with pentafluorophenyl acetate. These compounds were characterized on the basis of chemical analysis, IR, 1H NMR, 13C NMR and 19F NMR spectra. Tetrakis(2,2,2-trifluoro-1,1-dimethylethyl) titanate was the monomeric in nitrobenzene, but tetrakis(1H,1H-perfluor...

A colloidal rhodium has been prepared by reduction of rhodium(III) chloride with methanol in the presence of polyvinyl alcohol. The particle size distribution of the metallic rhodium is narrow ranging from 30 to 70 A with a maximum at 35 A. The colloidal dispersions in methanol-water solutions are effective for the hydrogenation of olefins at 30°C under an atmospheric hydrogen pressure.

The polymerization of benzene to poly(1,4-phenylene) (PPP) has been done successfully using copper(I) chloride and aluminium chloride as catalysts under oxygen. Since copper(I) chloride and aluminium chloride form a double salt (aluminium copper(I) chloride, AlCuCl4) and are soluble in benzene, a high homogeneity of the reaction system has been achieved and the polymerization reaction proceeds without any evolution of hydrogen chloride. The polymerization products contained an insoluble dark brown solid and a benzene-soluble tarry mass. The solid product has been determined to be PPP by comparison with an authentic sample. The product PPP was obtained in a yield of more than 100%, based on the molar quantity of copper(I) chloride, by controlling the quantity of aluminium chloride. For example, the treatment of benzene with aluminium chloride and copper(I) chloride (20:3:1 in molar ratio) under 1 atm of oxygen at 70 °C for 24 h gave PPP in a 187% yield, based on copper(I) chloride. This reaction could be c...

β-シクロデキストリン (β-CyD) を結晶状態でヘキサメチレンジイソシアナート (HMDI) と反応させることにより合成した縮合高分子を用いてβ-CyD膜を調製した. この膜を, 更に, HMDIで橋かけ処理することにより, 水中で長期間安定な膜を調製した, この橋かけ処理β-CyD膜は, 溶質の化学構造を反映した特異的透析能を示した. また, 橋かけ処理β-CyD膜を用いて, pH差を駆動力とする能動輸送を行うことに成功した.

The polymerization of aromatic compounds other than benzene (such as toluene, xylene, ethylbenzene, mesitylene, and biphenyl) was performed by using a copper(I) chloride–aluminum chloride–oxygen system which caused benzene to polymerize. Excess aluminum chloride, with respect to copper(I) chloride, was required for these compounds to polymerize, as was also true for benzene. For example, the treatment of toluene with aluminum chloride and copper(I) chloride (15:3:1 in molar ratio) under 1 atm of oxygen at 50°C for 24 h gave toluene polymer in 204% yield based on copper(I) chloride. This fact suggests that copper(I) chloride also worked as a catalyst in the case of the polymerization of toluene. The toluene polymer was obtained as both solid and liquid products, both of which were soluble in various organic solvents. The solid product has a complicated, crosslinked and “quinonoid-like” structure. On the other hand, the liquid product has a structure that is nearly identical with that of methylated poly(1,4...

A selective attack of dichlorocarbene at the para-position of phenolate has been achieved by using α-cyclo-dextrin and the reaction mechanism has been studied by the 13C-NMR and 1H-NMR spectroscopy. The attack of the carbene at the para-position of phenolate (82%) is dominant over the attack at the ortho-position (18%) in the presence of 0.15 mol dm−3 of α-cyclodextrin, which is in contrast with the predominance of the ortho-attack (59%) over the para-attack (41%) in the absence of α-cyclodextrin.

A new dry-type adsorbent for nitrogen monoxide was successfully prepared from an iron(II) salt and a chelate resin containing iminodiacetic acid moieties. The capability of adsorbing nitrogen monoxide depended greatly on the method of preparation. The very active adsorbent was prepared by mixing 31.4 mmol of iron(II) sulfate and a commercial chelate resin containing 21.0 mmol of iminodiacetic acid moieties; the mixture was dried after the solid parts had been washed with methanol. The resulting solid adsorbent could adsorb more than 99% of the nitrogen monoxide from 6 dm3 of nitrogen gas containing 1000 ppm of nitrogen monoxide within 25 min. This high capability for adsorbing nitrogen monoxide was derived from the increase in the surface area (43.1 m2 g−1) of the resin-immobilized iron(II) complex upon washing with methanol. The mechanism for the increase in the surface area is also discussed.

Solid adsorbents of carbon monoxide are prepared from aluminium chloride, copper(I) chloride, and a macroreticular type polystyrene resin by use of various solvents, and their resistivities against water vapor are investigated. The adsorbing capacities of the adsorbents prepared by use of carbon disulfide and dichloromethane remain virtually unchanged even after repeated (3–5 times) contacts of the adsorbents with nitrogen gas containing 10 mol% water with respect to the charged copper(I) chloride (water contents: 5600 and 4600 ppm). The adsorbents obtained with the use of benzene and toluene as preparation solvents, however, exhibit small but gradual decreases in the adsorbing capacities on the repeated contacts with nitrogen gas containing water. Scanning electron microscopy and energy dispersive X-ray microanalysis on the water-resistant adsorbents, prepared with the use of carbon disulfide and dichloromethane, show that the active species for the adsorption, aluminium copper(I) chloride, uniformly dis...

Chloroplatinic acid in an aqueous solution was reduced by hydrogen molecules or photo-irradiation in the presence of surfactants to produce colloidal dispersions of platinum protected by the surfactants. The particles of the colloidal platinum prepared by photo-reduction were smaller in size and more narrowly dispersed than those prepared by hydrogen-reduction. They worked as highly active catalysts for hydrogenation of olefins.

Irradiation of N-acetyldiphenylmethyleneamine (II) in toluene solution gave N-(1,1,2-triphenylethyl)acetamide and N-(1,1-diphenylmethyl)acetamide in 11% and 4.4% yields, respectively. The former is an addition product of toluene to the C=N bond of imine II, and the latter a hydrogenation product of II. The same kind of addition and hydrogenation products as those in toluene were obtained on irradiation of imine II in ethylbenzene, cumene, o-, m-, and p-xylene, mesitylene, p-methoxytoluene, and p-cyanotoluene, respectively. Two kinds of competitive reaction processes are proposed from the results of the substituent effects for the phenyl ring of toluene, the effect of the additives such as sensitizers and quenchers, and the dependence of the photoreaction yields on the concentration of the additive. The photoreaction proceeds not only by the “chemical sensitization” mechanism derived from the ketyl radical of benzophenone, a hydrolyzed product of II, but also by the mechanism through the excited state of I...

β-Cyclodextrin (β-CyD) was covalently immobilized on silica gel by chlorination of silica gel with thionyl chloride or silicon tetrachloride, followed by the reaction of the resulting chlorinated silica gel with β-CyD in pyridine. The amounts of the immobilized β-CyD were 8×10−5 to 1.4×10−4 mol per 1 g of the β-CyD–silica gel composites. On heating, the composites did not exhibit weight decrease up to 250 °C. The β-CyD in the composites formed 1 : 1 complex with phenol in aqueous solutions, and the equilibrium constant for the dissociation of the complex was 6×10−3 mol dm−3 at 25 °C. The immobilized β-CyD exhibited catalytic activity in the cleavage of 4-nitrophenyl acetate at 25 °C, pH 8.7.

A novel adsorbent of carbon monoxide (CO) is prepared by stirring copper(I) chloride and a macroreticular type polystyrene resin having amino groups in acetonitrile, followed by removal of the liquid phase at 5 mmHg, 80 °C. The adsorbent rapidly adsorbs carbon monoxide from 9 : 1 carbon monoxide–nitrogen mixture at 20 °C under 1 atm. The adsorbed carbon monoxide is readily desorbed by heating the adsorbent to 80 °C under 1 atm or by reducing the partial pressure of carbon monoxide to 5 mmHg at 20 °C. The CO adsorbing capacity (15.9 mmol) of the adsorbent composed of 10.0 g of the resin and 70 mmol of copper(I) chloride is 5.7 times as large as the carbon dioxide adsorbing capacity (2.8 mmol). The efficient adsorption of carbon monoxide by the present adsorbents is attributed to coordination of carbon monoxide to the copper(I) ions which coordinate the amino residues in the resin. The carbon dioxide adsorbing capacity (2.8 mmol) of the adsorbent is much smaller than that (8.3 mmol) of the resin without cop...

Photoreduction of N-Acetyldiphenylmethyleneamine (1) in 2-propanol was studied both by the ESR spectroscopy of irradiated imine 1 in a matrix solvent at −196 °C and by the deuteration analysis of acetone formed from 2-propanol-d in the photoreduction process. The ESR spectrum consists of a broad singlet and a quartet. The latter is assigned to the CH3CH(OH)\dotCH2 radical, which can be produced by β-hydrogen abstraction by the excited imine 1 from 2-propanol, but not by the excited benzophenone. Formation of acetone-d on irradiation of 1 in 2-propanol-d suggests that the imine 1 in the excited state has a hydrogen abstracting character.

Colloidal platinum protected by polymerized micelle was prepared by photoreduction of chloroplatinic acid in the presence of unsaturated surfactants and the subsequent UV-polymerization of the surfactants. This colloidal platinum acts as an active catalyst for photochemical hydrogen generation from water in the system of EDTA/Ru(bpy)32+/MV2+.

Active carbon-supported aluminium copper(I) chloride (AlCuCl4) is prepared by mixing active carbon with toluene solution of AlCuCl4, followed by the removal of the liquid phase at 6 mmHg, 100 °C. The active carbon-supported AlCuCl4 rapidly adsorbs carbon monoxide (CO) at 20 °C under 1 atm from 9:1 CO–N2 mixture and the equilibrium molar ratio of adsorbed CO to AlCuCl4 is 1.03. Adsorbed CO is desorbed either by reducing pressure or by elevating temperature. In the second adsorption, which is carried out after the desorption at 6 mmHg, 20 °C for 10 min, the molar ratio of adsorbed CO to AlCuCl4 is 0.51. The molar ratios are constant at 0.51 in the third and later adsorptions. The CO adsorbing ability of the active carbon-supported AlCuCl4 remains virtually unchanged on repeated contacts with nitrogen gas containing 9000 ppm of water.

Photoirradiation of anthracene in benzene in the presence of oxygen gave predominantly a photodimer of anthracene, and very little oxidation product. Similar irradiation of anthracene in bromobenzene, however, produced 9,10-anthraquinone in high yield. The yield of anthraquinone increased in the presence of a heavy-atom solvent such as bromobenzene, p-dibromobenzene, 1,3,5-tribromobenzene, 1-bromopropane, and dibromomethane in proportion to the sum of squares of the spin–orbit coupling parameter ζ of the solvent molecule. This relationship indicates an external heavy-atom effect on the photooxidation of anthracene. The mechanistic investigations suggest the involvement of singlet oxygen, anthracene peroxide, and a radical intermediate in the formation of anthraquinone.

Irradiation of N-(diphenylmethylene)acetamide (N-acetyldiphenylmethyleneamine, 1) in cyclopentene gave N-[1,1-diphenyl-1-(cyclopenta-2′-enyl)niethyl]acetaniide, the addition product of cyclopentene to the C=N bond of imine 1, in 31% yield. The photoreaction of 1 was observed in other cyclic and acyclic olefins. The reactivity of the olefins decreases in the order; cyclopentene>cyclohexene>cyclooctene>2-pentene\simeq2-hexene. The photoreaction is promoted by the presence of the heavy atom solvent or the sensitizer. The mechanism of photoreaction is discussed in terms of the excited triplet state of the imine.

The alkyl hydrogens of N-(2-alkyldiphenylmethylene)acetamides were found to be readily replaced with deuterium on irradiation in deuteriomethanol (CH3OD). It is proposed that the deuteration proceeds via an enamide isomer produced by intramolecular hydrogen transfer from the o-alkyl group to the excited C=N double bond. An intermolecular hydrogen atom abstraction pathway was excluded because neither N-(4-methyldiphenylmethylene)acetamide in deuteriomethanol(CH3OD) nor diphenylmethane in deuteriomethanol(CH3OD) in the presence of N-(diphenylmethylene)acetamide was deuterated. Intramolecular hydrogen abstraction is essential for the deuteration, because no deuteration occurs on irradiation of 2-methylbenzophenone semicarbazone which undergoes no photoreduction. The difference in reactivities of the ortho-substituted imines between in solution and in a rigid matrix is discussed from the viewpoint of syn-anti isomerization.

β-Cyclodextrin forms the 1:1 inclusion complex with Crystal Violet, Methylene Blue, Methyl Orange, or Congo Red in water. On the other hand, γ-cyclodextrin forms the 1:2 complex with Crystal Violet, Methylene Blue, or Methyl Orange, while the 1:1 complex is given with Congo Red. The one host-two guest complexations are shown on the bases of the changes of the electronic spectra, dependence of induced circular dichroisms on the concentrations of dyes, and the continuous variation methods with induced circular dichroism. The dissociation constants for the 1:2 complexes are determined with the improved Benesi-Hildebrand equation. Alternation between the 1:1 and 1:2 complexation is discussed in terms of the cavity size of cyclodextrin and the aggregation character of dye.