Zirconium oxide is stable and has been rarely used as a material for catalyst except for a carrier. Recently, some high catalytic activities of the hydrous zirconium oxide have been found. It catalyzes esterification, amidation, and acetalyzation. It also catalyzes a reduction of carboxylic acids to aldehydes with hydrogen gas. Ketones, aldehydes, carboxylic acids, esters, and nitriles are readily reduced to the corresponding alcohols with 2-propanol. It is worthy of remark because it implies an extension of the so-called Meerwein-Ponndorf-Verley reduction. The surface acidity of the oxide is weak and the reaction is applicable to acid-sensitive compounds.
The ene-type chlorination of benzyl prenyl ether (1 a) and benzyl geranyl ether (1 b) with hypochlorous acid gave allylic chlorides (2) in good yields. Allylic chlorides (2) reacted with Grignard reagents such as isoamylmagnesium bromide (2 a) and n-butylmagnesium bromide (2 b) in the presence of CuCl to give γ-ross coupling products (5) and (6) in high regioselectivities. Reactions of allylic chlorides (2) with prenylmagnesium chloride (2 c) were subsequently conducted in the presence of CuI to obtain the cross coupling products (4), (5) and (6).
The preparation and properties of a homologous series of sodium salts of alkyl pentaerythritol ether sulfates, containing 12, 14, 16 and 18 carbon atoms are presented. The sodium salts of alkyl pentaerythritol ether sulfate, possessing two primary hydroxy groups and a sulfate group as hydrophilic portions, were prepared by sulfation of the corresponding alkyl pentaerythritol ethers obtained by the etherification reaction of pentaerythritol with alkyl bromide. These surfactants showed excellent properties in aqueous solution such as lower cmc, higher stability toward calcium ions and low Krafft points. They were noted to function as highly effective calcium soap dispersing agents.
An oil gel was formed in a ternary system of sodium-montmollironite (Na-Mon), nonionic surfactant (SAA) and oil. Formation of the oil gel was caused by formation of an inclusion compound functioning as an SAA/Na-Mon binary system. The SAA having about 8 for an HLB value was easily taken in by the interlayer (silicate layer) of Na-Mon. From X-ray diffraction measurement, basal spacings of Na-Mon increased with the amount of SAA. The basal spacings of inclusion compounds were constant at an SAA/Na-Mon weight ratio of 1/1. Inclusion compound formation was completed when the adsorption of SAA in the interlayer of Na-Mon was saturated with a monomolecular layer at a 1/1 weight ratio. The inclusion compound swelled on adding an oil such as liquid paraffin (LP). with subsequent formation of the oil gel. X-ray diffraction indicated regular diffraction peaks in the stable and rigid oil gels. The structure of the swollen compound was lamellar with basal spacing ranging from 5060 Å. This interlayer swelling occurred with the inclusion of about 26 wt% of LP in the interlayer of the inclusion compound (SAA/Na-Mon).
An organophilic-montmollironite (Or-Mon) was prepared by a cation-exchange reaction between sodium-montmollironite (Na-Mon) and dioctadecyldimethylammonium chloride (DODAC). The cation exchange amount of DO-DAC in the Or-Mon was 80 meq/100 g-Na-Mon. This corresponds to the cation exchange capacity (CEC) of Na-Mon. The basal spacing of the Or-Mon was 26.75 Å, which could be explained by the formation of a single layer complex with the alkyl chain lying parallel to the silicate surface of Na-Mon. The Or-Mon easily adsorbed a nonionic surfactant (SAA) with an HLB value of about 8. The inclusion ratio of SAA to Or-Mon was 0.2/1.0 in weight, and the inclusion compound (SAA/Or-Mon) had 36.78 Å for the basal spacing indicating monolayer adsorption of DODAC into the silicate layer of the Na-Mon interface. SAA/Or-Mon swelled in an oil such as liquid paraffin, resulting in the formation of a gel. The swelling of SAA/Or-Mon may possibly have been induced by entrance of the oil into the interlayer of the SAA/Or-Mon.
Three types of catalysts, (A) chemically mixed catalyst activated in hydrogen after calcination, (B) chemically mixed catalyst activated in hydrogen without calcination, and (C) impregnated catalyst activated in hydrogen without calcination, were prepared. Their properties were investigated and compared, so as to elucidate the reasons why type (B) catalyst is the most effective for the formation of cyclohexene in the partial hydrogenation of benzene. Measurements of TGA, FT-IR, XRD, EM, hydrogen and carbon monoxide adsorptions indicated differences among the three types of the ruthenium catalysts : (1) type (B) catalyst contains diols used in its preparation, (2) active components (Ru, Cu) in the type (B) catalyst are highly dispersed compared with the other two catalysts, (3) the hydrogen absorption capacity of type (B) catalyst is much lower than its carbon monoxide absorption capacity, and (4) the carbon monoxide absorption capacity of type (C) catalyst is essentially the same as its hydrogen absorption capacity. From these findings, the diols remaining in type (B) catalyst following activation are considered to help prevent active components from aggregating by linking them to a support (Si) as a bridging ligand and to depress the formation of cyclohexane by reducing the hydrogen absorption capacity of ruthenium through coordination of the hydroxy groups. Type (B) catalyst is thus concluded to give high activity and cyclohexene yield in the partial hydrogenation of benzene.
The effects of residual acetyl group rates of poly (vinyl alcohol) s (PVA) on the stability of pyrithion zinc particle (Zpt) dispersion were examined. With decrease in the residual acetyl group rate of PVA, Zpt dispersion became less stable in sodium dodecyl sulfate (SDS) solution. However, in NaCl solution, the residual acetyl group rate of PVA had no effect on Zpt stability. The amount of SDS adsorbed on PVA and that of PVA on Zpt were determined. When the residual acetyl group rate of PVA decreased, the amount of SDS adsorbed on PVA was noted to decrease and that of PVA on Zpt to increase. The PVA-SDS complex was prepared for use as a dispersing agent. The stability of Zpt dispersed by this complex in NaCl solution was studied and found to depend on the quantity of the PVA-SDS complex present. These results indicate that PVA may be concluded to form complexes with SDS at acetyl groups by which Zpt dispersion is stabilized.