Surface properties of calcium tungstate powder (CaWO₄) prepared by interfacial reaction method (I. R. M.) were investigated, and the powder were found to be different from those of commercial CaW04 powder in the surface properties. The CaWO, powder prepared by I. R. M. was apparently hydrophobic, but it was shown by heat of immersion that the powder was polar solid. The surface of the CaWO₄ particles was observed to be porous by scanning electron microscope. The shape of the CaWO₄ particle is spherical, and the particle diameter is in the range of 1-10 p, the average 4.9 p. The specific surface area obtained by N2-adsorption is 24.5 m2/g; this value is about 100 times as larger as the calculated value from the particle size. The pore distribution obtained from water vapor adsorption isotherm (at 18°C) shows that the pore radius is in the range of 5∼200 A, the maximum being at 6070 A. The amount of the adsorbed Methylene Blue monolayer on the CaW04 surface is 1.49 x 10-5 g/m2, which is 1/3 of that of the commercial one. These results suggest that the CaWO₄ powder prepared by I. R. M. has porous surface, and that the external surface of the particles is hydrophobic but the internal is hydrophilic.

View full abstract

Phenol solution was continuously oxidized by supplying ozonized oxygen gas irradiation with a high-pressure mercury lamp. The decomposition under products and their ratios were determined by means of liquid chromatography. The reaction rate satisfied the following equation.
-d[P]/dt=k[P]0.44=k'[P]0.5=k" [O₃][P]0.5 (mol/l/sec)
Where k'=0.63 exp (-3.18 x 103/ T), k"=1.24 x 104 exp (-3.18 x103/T). The decomposition was accelerated by increasing the concentrations of potassium hydroxide at 26°C:
[P]KOH=0-[P]=[P]t=0{1-exp (-1.3 x 103[KOH][O₃]t)} The dependence of variation of each product upon the reaction time indicates that the decomposition proceeds consecutively.

View full abstract

The photographic senitivity of sulfur-sensitized cubic AgBr emulsion is maredly increased by adding 5-methyl-1, 3, 4, 7 a-tetraazainden-7-ol (compound [1]) and its related compound to the emulsions. It was found from infrared absorption spectra that these compounds are in an anionic form adsorbed on AgBr. The pl ci value of compound [1] is 6.27. The sensitization by compound [1]is accelerated with increasing pH and decreasing pAg of the emulsions. Only the tetraazaindenols, adsorbed on AgBr grains, can markedly increase the photographic sensitivity of the emulsions. It was found that these compounds, adsorbed on AgBr grains, can relate to the observed sensitizing phenomena. A probable mechanism for the sensitizing phenomenon has been discussed.

View full abstract

In the solid-solid reaction between MgO and V2O₃ at low temperature in H₂ atmosphere, the existence of metastable spinel-type materials was suggested by the X-ray diffraction study.
The reaction process was followed by means of measurement of lattice constant and analyses of intensities and profiles of diffraction peaks of the reaction products.
The lattice constant was found to increase by the increase in the reaction temperature. The observed integrated intensity of 222 reflection of the material fired at 1100°C was less than 60 percent of the calculated value. This result suggests the existence of metastable spinels involving cation vacancies on the octahedral sites. Asymmetrical profile of 111 reflection gives an evidence for vacancy segregation in the (111) plane of the spinel lattice.

View full abstract

Transitions of the Ca3(PO₄)2 (tricalcium bis (orthophosphate): T)-CaKPO₄ (potassium rhenanlite: PR) system was studied, in connection with the Ca, (PO₄)2-CaNaPO₄ system, by means of high temperature X-ray diffractometry and differential thermal analysis, and phase diagram was determined.
During heating, pure potassium rhenanite inverted from Q to a phase at 660°C. In the composition range from 6 to 98% of PR by weight, (βT+βPR), the stable phase at room temperature, inverted to (βT+αPR) at 645°C. In the range from 6 to 52.9 % of PR, (βT+αPR) changed into (βT+Ca5K2P4O16, compound "B") above 1090°C. The crystal of the compound " B " consisted of a- super lattice of a PR and inverted at higher temperature to αPR type solid solution which was a disordered lattice. In the range from 69.2 to 98% of PR, " B " was not formed on heating, but was formed on cooling at the temperature of Q T crystallization.
Relationship between transition temperature (Tt) into αPR type disordered lattice and vacancy content (Nv/ (NK + Nv)) estimated from the chemical formula was expressed as In {Nv/ (NK + Nv)}=-ΔHv/kTt+4ST/k, where Hv is enthalpy of random transformation of a vacancy and ST is thermal enthoropy. From the experimental results, it was evaluated that 4H and LIST for the system PR>52.9% were 30 kcal/mol and 18 cal/°K, respectively. These values for the system PR<52.9% were 15 kcal/mol and 8 cal/°K, respectively.
The relation between the cooling rate and the composition of the cooled products was also studied.

View full abstract

Change in dielectric loss tangent (tanδ) of thermally decomposed synthetic fluor-phlogopite crystal, KMg₃(AlSi₃O₁₀)F₂, was studied.
Tanδ of plate-like crystal preheated at 1150, 1200, 1250, 1300 or 1350°C in air for 1-10 days was measured at 105±2°C.
As for the specimens preheated at a given temperature, tan E generally increases with increasing fraction(α) of isothermal decomposition. This may be mainly due to the thinning of undecomposed crystal layer by thermal decomposition.
At a given α, tanδ decreases with increasing heat-treatment temperature. On the basis of SEM observation of the surface microstructure of specimens, this tendency is mainly due to a diminution of contact area between electrodes and surface of decomposed specimen by an increase in surface roughness.

View full abstract

The UV absorption spectra (200 to 370 nm, cell length: 1 cm) of rain water samples were studied in relation to nitrate ion concentration.
(1) Most of the spectra have no absorption maximum. The absorbance usually incrases with decreasing wavelength.
(2) Dissolved substances which absorb UV in rain water samples were divided into two groups, namely nitrate ion and others. The nitrate ion contributes to about 80% of the absorbance at 210 nm, and direct UV spectrometric determination of nitrate ion in rain water samples was possible by using the equation: NO^3-N(ppm)=(A₂₁₀-0.03)/0.66.
(3) The absorption spectra and the relationship between A₂₁₀ and A₂₁₀/A₂₂₀ of rain water samples were similar to those of river water samples. In the case of river water samples, the direct UV spectrometric determination of nitrate ion is possible when the relation, A₂₁₀/A₂₂₀ ≥ 1.75 is set up, while in rain water samples it is possible irrespective of the A₂₃₀/A₂₂₀ ratios.

View full abstract

Cathodic reduction of cinnamaldehyde (CA), being as a representative of a, f3-unsaturated carbonyl compounds, has been studied in solutions of acetonitrile (AN) in order to examine the effect of intermediate formation of ion-pairs between organic anion species and metallic cations, on the overall reaction pathways. At a dme, CA is reduced in dry AN exhibiting two well defined one-electron waves and an additional rather indistinct wave. The last wave may be caused by dimeric compound(s) formed after protonation of anion radicals. When magnesium perchlorate (in the form of tetrahydrate) was added to the solution, the original first wave of CA shifts toward more positive side by about 0.4 V. The shift of the second wave compared with that of the first one, becomes appreciable at a slightly higher concetration range of Mg²⁺ ion. The potential shift is attributed to the formation of ion-pair between electrode products and Mg²⁺ cations.
The formation of these intermediate ionic associates leads to a remarkable change in reaction products. Product obtained from dry AN is merely tar, but, upon addition of water, the formation of tarry material decreases and several dimeric products are obtained. When equimolar amount of Mg²⁺ is present in the solution, both hydrocinnamaldehyde and trans-cinnamyl alcohol are obtained besides dimeric products.

View full abstract

The response of a electron capture detector (ECD) in various pulse conditions has been studied in order to reveal the influence of background current (4) on the sensitivity of electron capturing compounds.
The variations of Ib with pulse width (tw: 0.1∼10 μsec) were measured in various pulse periods (tp: 100∼2000, μusec) at 30 V (Fig.1), and then at different levels of pulse amplitude (Fig.2). The plateau values of /b-tw curves decrease linearly with increasing tp (Fig.3). On the other hand, the number of electrons (Ne-) in the ECD cell increase, with increasing tp until saturation at about 2000 /μsec (Fig.4). The magnitude of the over-all rate constant of reactions with electrons (k, ) and the production rate of thermal electrons (kpRp) are 1.1 X 10³/ sec and 1.73 X 10¹⁰ electrons/sec, respectively.
The variations of the sensitivity of electron capturing compounds with 4 are as follows: In the shbulder of each /b-t, curve, the sensitivity becomes a maximum, and the maximum value and-its t, increase with increasing tp (Fig.5). In the plateau region, as the electron concentration in the ECD cell approaches to the steady state with increasing tp, the sensitivity increases with increasing tp up to 1000∼1500, μsec (Fig.6).

View full abstract

A method by the measurements of lattice constants (a0, co) and intensity ratio has been developed to determining the composition of a magnesium-zinc-containing 8-eucriptite solid solution in glass-ceramics, which is a pseudo-quarternary solid solution of SiO^2-Mg_1/2AlO^2- ZninAl0, -LiAlO₂.
Standard samples of the solid solution within the range of 65-80 mol% SiO₂, 0-10 mol% Mg_1/2A102, and 0-10 mol% Znu2A1O₂ (the remaining: LiA1O₂) were prepared from highpurity materials by the " glass-crystallization " technique. The lattice constants were determined from the angular positions of the centers of gravity of 206 and 212 lines. The intensity ratio (I₁₀₀/I₂₁₀₀) was obtained from the products of each peak height and half-maximum width.
The values of c/o, c0, and I₁₀₀/I₂₁₀₀ depend unequivocally on the concentrations of SiO₂, Mg_1/2AlO₂, and Zn_1/2AlO₂, respectively. Three methods are described for determining the composition of the solid solution from the three-dimentional correlation between the composition and these three parameters. The analysis of the solid solution in a commercial glass-ceramic is also given by the proposed methods. The estimated standard deviations of the determination from one measurement were 0.6 mol %, and the time required for analysis was about 1 hr.

View full abstract

Photochemical reaction of diethyl p-phenylenediacrylate (p-PDAEt) in solution was investigated. It was observed that the reaction proceeded in various ways depending on concentration of solution, solvents and wavelength of irradiation light. That is, in dilute solution (1.8 x10^-3 mol/l), cis-rans isomerization takes place, while in concentrated solution (0.72 mol/l), cyclobutane ring formation occurs.
In highly concentrated acetonitrile solution p-PDAEt undergoes oligomerization giving oligomers composed of t-3, t-4-diphenyl-r-1, c-2-cyclobutanedicarboxylic acid type cyclobutane rings (Fig.2-B). In order to clarify the reaction mechanism, UV and flouresence spectra of dilute and concentrated solutions were measured (Figs.3 and 4). In the latter spectra, red shift and a flouresence peak from an excimer have been observed. Therefore, the possible reaction mechanism for the stereoselective formation of cyclobutane ring is considered to involve an excimer.

View full abstract

The reactions of secondary halooctanes with ethylene oxide in the presence of zinc halide were studied. Insertion of ethylene oxide into halogen-carbon bond of secondary halooctanes gave 2-haloethoxy derivatives. The insertion product from the reaction of secondary bromooctanes [1] with ethylene oxide consisted of 2-(2-bromoethoxy)octane [2], 3- (2-bromoethoxy) octane [3] and 4-(2-bromoethoxy)octane [4].
In the reaction of 2-bromooctane with ethylene oxide, the maximum yield of secondary (2-bromoethoxy)octanes was obtained at the temperature of 130°C and the suitable mole ratio of zinc bromide to 2-bromooctane was O.03-0.1.
The isomer distribution of [2], [3] and [4] was determined in each reaction of ethylene oxide with 2-, 3- and 4-bromooctane, and found to be in order of[2]>[ 3]6gt;[4] in the reaction of any secondary bromooctane with ethylene oxide at 130°C. However, at 110°C the introduction of 2-bromoethoxyl group mainly occurred in the position to which bromine was originally attached.

View full abstract

he reactions of benzyl Grignard reagents with acyl halides have been investigated under various conditions. The reaction with acetyl chloride affords benzyl methyl ketone [1]and methyl o-tolyl ketone [2]. The yield of [2] decreases with the increase of the solvent basicity and of the ionic character of C-M bond in the order of C-Al<C-Mg<C-Li. The reaction with the other acyl halides afforded both normal product C and o-tolyl product [2], similarly in the case of acetyl chloride.
The yield of o-tolyl product [2] decreased in the order of CH₃COCl> (CH₈)₂CHCOCl> C₆H₅COCl> t;C₆H₅COCl>. This order corresponds to that of the reactivity of the acyl halides. The reaction mechanism was discussed on the basis of these findings in comparison with the reaction of aldehydes with the Grignard reagents.

View full abstract

9, 10-Phenanthrenequinone has been shown to react with primary amine to form oxazole and imidazole derivatives; phenanthrenequinone reacted with benzylamine to give 2-phenylphenanthro[9, 10-c/]oxazole and 1-benzy1-2-phenylphenanthro[9, 10-d]imidazole; and the reaction with butylamine gave 2-propylpheananthro[9, 10-d]oxazole. In the presence of an aldehyde, the reaction of phenanthren. equinone and benzylamine gave phenanthroimidazole and phenanthrooxazole bearing 2-substituent originated from the aldehyde. Aldehyde having an electron withdrawing substituent such as p-nitrobenzaldehyde was more easily incorporated into the products.

View full abstract

The equilibrium adsorption of C. I. Disperse Red 1 and Red 15 on cellulose acetate from aqueous ethanol solutions has been investigated by means of partition coefficient and solubility. Measurements were made on the 100∼60 vol% aqueous ethanol solutions at temperatures ranging from 30 to 60°C. Partition coefficients were determined from adsorption isotherms. Heats of dyeing and heats of solution were calculated from the Arrhenius plots of the partition coefficients and the solubilities, respectively.
In spite of the difference between Red 1 and Red 15 in the effect of the ethanol concentration on the partition coefficient and solubility, approximate linear correlations are given for both dyes between logarithms of both the parameters and between the heats of dyeing and heats of solution. The values for 100% ethanol, however, deviate markedly from the linearity. The difference of the behavior of 100% ethanol from those of solutions below 90 vol % may be due to an unusual interaction between water and ethanol.

View full abstract

The adsorption characteristics of Hg (II) ion on several activated carbons prepared from various sources by different activation methods have been studied. From effects of pH, temperature and properties of activated carbons (specific surface area, amounts of surface oxides) on the adsorption and desorption of Hg (II) ion, the following conclusions were obtained.
(1) Activated carbons prepared from wood, coconut shell and coal by the steam activation method have a high adsorptive. ability for Hg (II) below pH 5 in a HCl medium but the ability is low at pH above 5. The activated carbon prepared from wood by the ZnCl₂ activation method has a high adsorptive ability for Hg(II) even at pH above 5.
(2) Both activated carbons prepared by steam and ZnCl₂ activation methods adsorb HgCl₄^2- reversibly in a HCl medium. Above pH 7 the activated carbon prepared by the steam method adsorbs Hg 10 mainly by the irreversible adsorption which accompanies reduction of Hg(II) on the surface of the activated carbon. The activated carbon prepared by the ZnCl₂ method adsorbs Hg (II) mainly by the reversible adsorption of Hg (OH)₂
(3) The adsorption characterstics of Hg (II) on activated carbons are affected a little by the kind of sources of activated carbons but are varied greatly by the activation method of carbon.
(4) Contents of acidic and basic surface oxides of activated carbons also affect the adsorption characteristics of Hg (II) on activated carbons,

View full abstract

The interactions between sodium chondroitinsulfate-C (Ch-Na) and organic salts were studied by means of viscometry, potentiometric titration, precipitation experiment, and conductometry. The organic salts used in this study were methyl- (MAO), ethyl- (EACl), butyl- (BACl), hexyl- (HACl), octyl- (OACI), decyl- (DeACl), and dodecyltrimethylammonium chloride (DTACl). The lowering of the reduced viscosity of Ch-Na or the apparent pK, of the corresponding polyacid due to the added salts is in the following order:
MACl>EACl>BACI>HACI>OACI, and DTACl>DeACl>OACl.
The experimental results are interpreted in terms of the hydrophilic-hydrophobic balance of the organic salts. For the organic salts having alkyl group shorter than that in HACl, the salt effect is mainly due to the electrostatic interaction. The tendency of hydrophobic interac-tion between the organic salts and the polyion becomes a dominant factor in the case of longer-chain salts. The interpretation was confirmed by the results of precipitation and electrical conductance measurements.

View full abstract

The method of a French Patent for the polymerization of 2, 6-dichloro-4-bromophenol was applied to the condensation polymerization of 2, 4, 6-tribromophenol. By IR or NMR spectroscopic measurement, the polymer structure was found to be more linear than that obtained by other methods. The effects of various reaction conditions on the polymerization were studied. The yield or M. W. of the product reaches a maxium value after several hours and then decreases gradually with time. Therefore, a quinone-ketal redistribution mechanism may be suggested. DMSO, as a solvent in the reaction mixture, is found to have great influence on the product, especially it increases the lineation of the structure. These findings were explained in terms of the formation of polymeric complexes between DMSO and monomer in a molar ratio of 1 1. The complex formation was considered to control the reactivity of the monomer at the ortho position. Consequently, polymers with high M. W. and linear structure would be expected. The complex formation was also discussed in terms of the measurement of the electric conductivity or UV spectra of the reaction mixture.

View full abstract

p-Benzoyloxystyrene, which is a polymerizable ultraviolet absorbant, was grafted onto cotton fibers with various initiators and the resistance of this grafted cotton fibers against ultraviolet ray was compared with one another. When cerium(IV) ammonium nitrate is used as an initiator, grafted fibers with short branches are obtained. On the other hand, in the case of a, ex' -azobisisobutyronitrile or ammonium peroxosulfate, grafted cotton fibers with long chains are produced in limited amounts. In the former case, either grafting efficiency or ultraviolet-resistance is superior to that in the latter one. From these studies, it was suggested that cerium(IV) ammonium nitrate is the most preferable grafting initiator.

View full abstract

The tight copper oxide surface containing Cu₂0 and CuO was obtained by immersing degreased-copper plate free from oxide, in a bath consisting of 250 ml of boiling water, and 1 ml of 0.4 N sulfuric acid containing 5% of H₂O₂ for 2 min. Then, the above copper plate was immersed in an aqueous solution of disodium salt of 6-anilino-1, 3, 5-triazine-2, 4-dithiol (AF 10-3 mol/l) for 10 min at 50°C. The resulted copper plate was overlaid with the blending sheet (CHC 100, C 40, AF 1.5, trithiocyanuric acid (F) 0.5, CaCO₃ 10 phr) and cured at 160°C for 40 min under 100 kg/cm² to give an adhesion with a peel adhesion of 14.6 kg/cm.
The adhesion force is assumed to be resulted from the formation of copper mercaptide among

View full abstract

2-Dimethylaminoethyl methacrylate (DM) was graft copolymerized onto (hydroxyethyl)cellulose (HEC) by the use of Ce-salt and H₂O^2-Fe2+ as an initiator. The flocculating action of the purified cationic graft copolymers (HEC-DM) toward both kaolin and fine cellulose fiber suspensions was investigated in comparison with that of poly DM (PDM) and nonionic HECacrylamide (AM) graft copolymers. The flocculating action of HEC-DM was as follows: (1) Upon comparison between graft copolymers, whose grafted branches have the same molecular weight in a similar manner as the flocculating action of HEC-AM, HEC-DM is scarcely affected by a small number of branches (1-2) per one HEC molecule. (2) HEC-DM is superior to HEC-AM for the clarification of suspensions; however, the former is inferior to the latter for the acceleration of sedimentation, when Mn of HEC-DM and that of nonionic HEC-AM are the same. (3) The sedimentation rate with HEC-DM increases with increasing Mn; however, an increase in sedimentation rate due to HEC-DM is smaller than that due to HEC-AM. (4) The effect of Mn on the clarification with HEC-DM is similarly small as that with HEC-AM. (5) The suspensions tend to disperse easier at a large dosage of HEC-DM than at a dosage of HEC-AM. (6) Whenfin of graft copolymers and that of homopolymers are the same, the flocculating action of HEC-DM and that of PDM are almost the same; however, the above action of HEC-AM is superior to that of PAM. (7) Property of HEC-DM or PDM changes with temperature; suspension disperses at a low temperature and flocculates at a high temperature.

View full abstract

Tsushima, Okayama-shi 700 Japan The investigation was carried out to prepare activated carbon in high yield from waste plastics, e. g., copolymers of poly (vinylidene chloride) (PVDC)-poly(vinyl chloride) (PVC) or poly (acrylonitrile) (PAN), PVC, polycarbonate (PC), polyester, polyethylene (PE), polystyrene (PS), etc.
The thermal decomposition characteristics (initiation temp. and rate pattern of weight decrease), possibility of carbonization and the effects of activation during carbonization process of these plastics were examined at increasing or constant temperature below 1000°C in flowing N2, CO₂, H₂O (10%)-N2, air, Cl2 and/or HCl chiefly to elevate the activated carbon yield Y (g/g (plastic)) and specific surface area Sg (m2/g(activated carbon prepared)).
The results obtained are as follows:
(1) From PVDC copolymers and polyester, activated carbon (ca.700 m2/g (SO) is obtained merely by the thermal decomposition below 700°C. From PVC and PC, activated carbon 1000 m2/g (Sig)) is prepared by the activation in H₂O or CO₂ stream at temperatures higher than 800°C after carbonization.
(2) The carbonization in Cl2 stream is very efficient. For example, from PS, which does not give carbon by the thermal decomposition, activated carbon (2050 m2/g (Sg)) is obtained by the Cl2 treatment.
(3) The facility of preparation of activated carbon is in the order of. PVDC-copolymers >PVC> PC, polyester, from the comparison of their carbon yields, rac (cec: carbon content in plastic).
(4) Iodine adsorbed amount per unit sursce area of the above activated carbon is comparable to that of commercially activated carbon.
(5) By plotting the surface area Sp=(YS, ; m2ig (plastic)) or Se (=Spicre; m2/g (carbon in plastic)) vs. Y (or rac) or Sg, the relations between Y and surface-area developing rate (change of Sg with change of pore diameter distribution) during the activation process can easily be elucidated. These diagrams are very useful for the reasonable comparision and/or judgement of the preparation conditions.

View full abstract

When HC1 diffuses into a gelatin gel, the diffusion coefficient (D) is greatly dependent on the concentration of HC1. D is very small when the concentration of HC1 is lower than that of HC1 which saturates a basic group of a gelatin. Above this concentration, D becomes larger than that of HC1 in an aqueous solution. The large D may be caused by ( 1 ) moving of the boundary between a diffusing solution and a gel by swelling or sol-forming of a gelatin gel, or lowering of the gelatin concentration in the gel near the boundary by swelling, ( 2 ) increase in apparent concentration due to further addition of HC1, which is caused by the fixation of HC1 on a basic group in a gelatin gel.

View full abstract

The photochemical reaction of 2-amino-1, 4-naphthoquinone in water was investigated by using the light of wavelength 254 nm. As a product, 2-amino-3-hydroxy-1, 4-naphthoquinone was obtained, but 2-amino-1, 4-naphalenediol, a reduction product of 2-amino-1, 4-naphthoquinone, was not obtained.
This phtochemical reaction seems to proceed by the nucleophilic addition of OH- anion from water to the quinone in a 7r-e excited state (Scheme 4).

View full abstract

The oxymeithylenation of p-chloro- [1a], pentachloro- [ 1b] and 2, 4, 6-tribromophenols [1], ethyl P-hydroxybenzoate [1d], 4-hydroxy-2-methoxybenzaldehyde [1e], 1-[1f] and 2-naphthols [1g] and catechol[1h] were studied in a noncatalytic heterogeneous reaction. ystem. Thus bis(aryloxymethyl) ethers [2a∼h]which were difficult to prepare by conventional methods, were obtained in good yields when [1a ∼h] and a solution of sodium (or potassium) hydroxide were added from separate inlets regulating 4 to lower the, concentrations of [1a ∼h] into a DMSO solution of bis(chloromethyl) ether.

View full abstract

The formation of charge-transfer (CT) complexes of substituted imidazoles and oxazoles with chloranils have been spcetrometrically studied. The absorption spectrum of the complexes shows that interactions between 2-arylphenathro[9, 10-d]oxazoles and chloranil are less than those of 2-arylphenanthro[9, 10-d]imidazoles and chloranil. The absorption maximum of the complex of 2-(p-methoxyphenyl)phenanthrooxazole shifted to longer wavelength than that of 2-phenylphenanthrooxazole, and 2-(p-nitropheny1)- phenanthrooxazole did not form the complex. The formation of CT complex of substituted 2 H- and 4 H-phenanthroimidazole was not observed. These results suggest that chloranil molecules interact mainly with imidazole ring rather than with the phenanthrene ring.

View full abstract

The chiral phosphines of sugar derivatives, 6-deoxy-1, 2: 3, 4-di-O-ispropylidene-6-diphenylphosphino-a-D-galactopyranose [1] and methyl 4, 6-O-benzylidene-2-deoxy-2-diphenylphosphinoa-D-altropyranoside [2], were prepared. Asymmetric hydrogenation of prochiral olefins (α-acetamidocinnamic acid, itaconic acid, atropic acid, tiglic acid) were carried out at room temperature under atmospheric pressure by using Wilkinson catalyst with [1]or[2]as ligands. Optical purities of hydrogenate products were generally low, and the highest enantiomeric purity of about 40% e. e. was obtained in the case of hydrogenation of tiglic acid by using the catalyst with [2].

View full abstract