In order to examine oxidation with Fremy's salt, 5-phenyl-1-naphthol (21) (mp 93-94°), 5-methyl-1-naphtol (22) (mp 93-94°), 5-ethyl-1-napthol (23) (mp 78-80°), and 5-isopropyl-1-napthol (24) (mp 68-69°) were prepared from 8-chloro-5-methoxy-3, 4-dihydro-1 (2H)-naphthalenone (4).
Diffusion rate constants of 23 compounds through an artificial lipid barrier were studied employing a Sartorius absorption simulator for barbituric acid derivatives (I). Acid dissociation constants and lipid-water partition coefficients were also determined spectrophotomerically. It was found that there was a parabolic dependence on log P for log k by applying equation (12).
Polygonatiin (IV), C33H40 5H2O, mp 215-217°, a new C-glucosylflavone, was isolated from the leaves of Polygonatum odoratum (MILL.) DRUCE var. pluriflorum (MIQ.) OHWI (Liliaceae) together with oosmosiin (I), vitexin (II), vitexin 2"-O-glucoside (III), and saponarin (V). The structure of polygonatiin was determined as vitexin 2"-O-sophoroside by chemical degradation and spectral measurements.
Gas chromatographic analysis of 5-methylcytosine in t-ribonucleic acid (tRNA) is reported. This method involves hydrolysis of tRNA with perchloric acid, neutralization with CG-4B resin (OH-form), selective elution of cytosine and 5-methylcytosine from Dowex 1 X2(HCOO- form), iodination of cytosine, trimethylsilylation, and injection into a gas chromatograph. This method requires only a few milligrams of tRNA, and can be performed within one day. Application of this method for the analysis of 5-methylcytosine in DNA was suggested. Analytical results of 5-methylcytosine in tRNAs from several sources indicated that tRNA extracted from tumor tissues contain less 5-methylcytosine than that from normal tissues.
The compaction behavior of powders in the centrifugal and vibrational fields was examined using calcium carbonate and sulfathiazole having different particle sizes. The apparent volume of the powder decreased with increasing acceleration of the bed. When the particle size was more than several μm, an approximately linear relation was observed on plotting the logarithm of the porosity effective for packing against logarithm of the average force acting upon a single particle. In the case of ultrafine powders, however, the values of porosity were found to be lower than those expected from the above relation, which may be due to the formation of agglomerates. The agglomerate number of these samples was estimated from the compaction data and also from the air permeation measurements.
Based on the report that 2, 4-bis (2-acetoxybenzamido) benzoic acid (AB-50) gives an anti-allergic effect, which was attributed to its membrane-stabilizing effect resulting in the inhibition of antigen-induced histamine release from the mast cells, interaction of 2, 4-bis (2-hydroxybenzamido) benzoic acid (AB-23), an active form of AB-50 in the body, with rat peritoneal mast cells was examined. Histamine release from the peritoneal cells induced by compound 48/80 was compared in the cells pretreated with AB-23 and those with a buffer solution alone, and less degree of histamine release was observed for AB-23-treated cells. Extent of the inhibition by AB-23 pretreatment depended on its concentration and also on the time and temperature of treatment. When the cells were incubated at 37°in the presence of AB-23 or 14C-AB-23, the inhibitory effect and the amount of radio-activity in the cells increased with the incubation time. On the other hand, when treated at 0°, the cells showed no inhibitory effect of the chemical and poor incorporation of 14C-AB-23. The inhibition of histamine release by AB-23 pretreatment was easily recovered, and responsiveness of the cells to compound 48/80 was restored by standing AB-23-pretreated cells at 37°but not by standing at 0°. Residual radioactivity within the cells pretreated with 14C-AB-23 progressively decreased while standing at 37°, whereas the radioactivity remained constant at 0°. These results indicated that AB-23 was incorporated into the cytoplasma and/or membrane of mast cells at 37°, but not at 0°, to inhibit the histamine release induced by compound 48/80.
The normal paraffins and triterpenes contained in the leaves of seven kinds of Quercus spp. (Q. stenophylla MAKINO, Q. myrsinaefolia BLUME, Q. glauca THUNB., and Q. gilva BLUME, Q. sessilifolia BLUME, Q. acuta THUNB., and Q. phillyracoides A. GRAY) were studied systematically. The normal paraffins in each plant consisted of the same heptacosane (C27), nonacosane (C29), hentriacontane (C31), and tritriacontane (C33). The ratio of normal paraffin components was similar in closely related plants. As a triterpene, eight known compounds (friedlin, epi-friedlanol, friedelanol, taraxerol, lupeol, β-amyrin, β-amyrin acetate, and friedelanol acetate) and three unidentified compounds (triterpene D-7, mp 244-245°, from Q. gilva BLUME, triterpene D-20, mp 212-215°, from Q. gilva BLUME, and triterpene E-6, mp 135°, from Q. glauca THUNB.) were isolated. Friedelin and epi-friedelanol were contained in all the plants, and lupeol was present in most of the plants. Especially, a large amount of friedelin was isolated from Q. stenophylla MAKINO. Lupeol was contained in a large quantity in Q. phillyracoides A. GRAY. The component of the white waxy compound, secreted on the back of leaves of Q. stenophylla MAKINO, was examined and the substance was almost entirely a mixture of wax and triterpenes. The principal ingredient of triterpenes was friedelin, same as in the extract of leaves.
The two triterpens, β-amyrin acetate and lupeol, were isolated from the leaves of Quercus glauca THUNB. (=Cyclobalanopsis glauca QERST.). An unidentified triterpene, E-6, was found to be a mixture of two triterpenes, I (major) and IX (minor), by the gasliquid chromatographic determination, and these compounds were separated by silica gel column chromatography. Triterpene I (C32H52O, mp 187-190°) is a new triterpene and was named cyclobalanone. Its structure was determined to be 3-oxo-24, 24-dimethyl-9, 19-cyclolanost-25-ene from its chemical reactions and by a physico-chemical method. Triterpene IX was identified as the known 24-methylencycloartanone.
Two triterpene acetates (V and I) were isolated from the leaves of Quercus gilva BLUME. V was obtained as a new compound from natural source. Its structure was determined as 24, 24-dimethyllanosta-9(11)-dien-3β-yl acetate by the physicochemical methods and chemical evidence. I was established as hop-17(21)-en-3β-yl acetate, which was previously obtained from Quercus spp.
New kaempferol glycosides, named multiflorin-A and -B, were isolated from the active fraction of a purgative drug, Rosa multiflora THUNB., together with kaempferol 3-α-L-rhamnopyranoside (III) and methyl gallate. Multiflorin-A and -B were determined to be kaempferol, 3-β-D-glucopyranosyl-(1→4)-α-L-rhamnopyranoside monoacetate (II) and kaempferol 3-β-D-glucopyranosyl (1→4)-α-L-rhamnopyranoside (I), respectively. Among these constituents, multiflorin-A has the strongest purgative activity.
Needle-like crystals of caffeine, the so-called whiskers, were found to grow on the surfaces of granules containing caffeine and some of ingredients during storage under accelerated conditions of temperature with time. Growth of the whiskers was promoted by ingredients in the granules which were glycyrrhizic acid, pluronic F68, and hydroxypropyl-cellulose (HPC-L), whereas growth was scarcely observed on the granules free from one of these ingredients. A great effect of humidity and temperature on the susceptibility to whisker growth was recognized. It was proved by microscopic observations and various experiments that caffeine whiskers were non-proper whiskers which grew at the fiber tip, not at the bottom, from caffeine molecules in the vapor phase surrounded by a crystal lattice, on the growth face of caffeine crystals.
The essential oil composition of the rhizome of Atractylodes lancea DC var. chinensis KITUMURA, a Chinese crude drug "Jin-changzhu, " was found to consist of four sesquiterpenoids. i.e., β-selinene (2), (-)-α-bisabolol (3), hinesol (4), and β-eudesmol (5) (major), and an acetylenic compound atractylodin (6) (second major). On the basis of the chemical correlation with(-)-β-bisabolene (8), (-)-α-bisabolol was elucidated as (-)-1′(S), 2 (ξ) -6-methyl-2-(4′-methyl-3′-cyclohexen-1′-yl)-5-hepten-2-ol (3). From the benzene extract of the rhizome of A. ovata DC "Chinese baizhu, " a furanosesquiterpene atractylon (1a). was isolated as the major component. The compositions of sesquiterpenoids and acetylenic compounds in two different groups of crude drug "zhu" ("changzhu" and "baizhu")were examined by gas chromatographic analysis, and this method of analysis was found to be useful for discrimination of the original plants of "zhu".
It was found that the thiamine hydrochloride exists in 5 crystalline phases (polymorphs and pseudopolymorphs). The most stable form is the monohydrate (I), which is common on the market. Comparison of the X-ray diffraction patterns showed that I is identical with the α-form reported previously. 3The metastable form (II) is an anhydrate and identical with the β-form in the same report. II shows a polymorphic transition at about 197° to III, which is stable at higher temperatures. III is also obtained by heating I at about 90° and is easily transformed to I by absorbing H2O in the air. IV, the unstable phase, is obtained by recrystallization from methanol and is confirmed to be a monomethanolate. IV is transformed to V, releasing methanol slowly in the air but rapidly at about 80°. V is liable to absorb H2O to become I in the air. All these results were deduced from X-ray diffraction, infrared absorption spectrometry, differential thermal analysis and thermogravimetric studies.
Treatment of methyl 4, 6-O-benzylidene-2, 3-dideoxy-2, 3-epithio-α-D-allopyranoside (I), methyl 4, 6-O-benzylidene-2, 3-dideoxy-2, 3-epithio-α-D-mannopyranoside (II), and methyl 4, 6-O-benzylidene-2, 3-dideoxy-2, 3-di-S-benzyl-2, 3-dithio-α-D-altropyranoside (XVII) with Amberlite IR-120 (H+) in 80% methanol, resulted in hydrolytic cleavage of each benzylidene group, followed by isomerization of these methyl pyranosides to the corresponding methyl furanosides.
Methods are described for the isolation of biologically active substances from rabbit skin tissues infected with vaccinia virus. The inhibitory activity on tetragastrin-stimulated gastric acid secretion found in the alkaline aqueous extract of the infected tissues boiled in acetone was concentrated by precipitation with ammonium sulfate and acetone. Further purification of the active material was carried out by chromatography over DEAE-cellulose and gel filtration over Sephadex G-75. The yield of the purified protein, Fr. I, was 2.25 mg from 1.0 kg of infected tissues, and Fr. I showed 77.2±8.4% (n=5)of inhibitory activity when doses of 5.0 mg/kg were administered intravenously into rats. This protein was also a potent inhibitor of gastric acid, gastric juice, and pepsin secretion, and ulcers induced by pylorus ligation. Molecular weight of Fr. I was 69000 by sodium dodecyl sulfate gel electrophoresis and gel filtration through Sephadex G-75. Amino acid analysis demonstrated 18 different amino acids, with high content of glutamic acid and proline. Another biologically active material was extracted with boiled aqueous phenol and fractionated with Dowex 50W chromatography. This material, contained uracil, xanthine, several amino acid-related substances, and nucleoside-related substance. Fr. d. Ornithine, ethanolamine, and Fr. d inhibited heat-induced hemolysis of rabbit erythrocytes, and Fr. d was also a potent inhibitor of chemotaxis of rabbit polymorphonuclei in vitro.
Xylenes were methylated with methanol on base-modified SiO2-Al2O3 catalyst at 250° by the use of a gas-phase heterogeneous flow method. On commercially obtained SiO2-Al2O3 trimethylbenzenes reached equillibrium composition at the reaction temperature among pseudocumene, hemimellitene, and mesitylene. In contrast, on ethylenediamine-modified SiO2-al2O3, mesitylene was not observed in the methylation products. Pseudocumene and hemimellitene produced from ο-and m-xylene were in a molar ratio of 6 : 4, and pseudocumene was obtained exclusively from p-xylene. The selectivity on these catalysts was examined by acidic properties of the catalyst and the distribution of trimethylbenzene isomers. The acid site of H0≤0.8 disappeared from the NH3-modified catalyst which showed selective methylation.
In order to examine the peri effect in the oxidation with Fremy's salt, 5-fluoro- (mp 135-136°), 5-chloro- (mp 134-136°), 5-bromo- (mp 136-137°), 5-iodo- (mp 136-137°), 5-methoxy- (mp 137-139°), 5-acetoamido- (mp 179-180°), and 5-nitro- (mp 168-169°) 1-naphthols were prepared by using reaction sequences which did not produce any positional isomers. 1-Naphthol itself and 1-hydroxyphenanthrene (mp 157-159°) were also prepared.
6-Halogeno-8-nitroquinaldies (III, IV, V) were synthesized by the reaction of 4-halogeno-2-nitroanilines with crotonaldehyde, in the presence of Sulfo-mix, boric acid, and ferrous sulfate. The nitroquinaldines were reduced with stannous chloride and hydrochloric acid to 8-amino-6-halogenoquinaldines (VI, IX, X). Under some reaction conditions, dichloro compounds (VII and VIII) were obtained. Thiocyanation of VI, VIII, IX, and X with ammonium thiocyanate and bromine in acetic acid solution gave the thiocyanated compounds (XI to XIV). Thiocyanation of VI to IX was examined by Huckel's molecular orbital method and a good agreement was seen between the theoretical and experimental result.