One of the available methods of measurement of the diffusion coefficient is the porous diaphragm method, which was introduced by Northrup and Anson and developed by McBain and Nakagaki. Their methods are based on diffusion model (1) in Fig. 1, namely they neglected the concentration gradient in liquid phases. We used the diaphragm method also but took the gradient into account, our model (2) is shown in Fig. 2. The equation and the boundary conditions of our model are given by eq. (1). Its solution is given by J. Crank as eq. (2) and (3), where h is constant. Now, h should be dependent upon D. From the consideration of mass transfer, we assumed h=kD and determined k as ca. 0.66 experimentally. So, eq. (3) is converted to eq. (6). Measure of the diffusion coefficient of caffeine in water is found on the graphical Integral of eq. (6).
The Perkin reaction of 2-thiophenecarboxaldehyde and 2-thiopheneacetic acid afforded two kinds of stereoisomers of 2, 3-bis (2-thienyl) acrylic acid (IV) ; α-form (IVa) and β-form (IVb). Amidation of these compounds produced cis-2, 3-bis (2-thienyl) acrylamide (IVa) and trans-2, 3-bis (2-thienyl) acrylamide (VIb) from IVa and only IVb from IVb. The same reaction of 5-nitro-2-thiophenecarboxaldehyde (X) and 2-thiopheneacetic acid also afforded two isomers of 2-(2-thienyl)-3-(5-nitro-2-thienyl) acrylic acid (III) ; α-form (IIIa) and β-form (IIIb). Amidation of these compounds also afforded the cis-(XIa) and trans-2-(2-thienyl)-3-(5-nitro-2-thienyl) acrylamide (XIb) from IIIa and only XIb from IIIb. That these compounds were mutual stereoisomers was proved by the measurement of ultraviolet (UV) and infrared (IR) absorption spectra, and dipole moments.
A total of 62 kinds of compounds to be derived from lichen components by decomposition were synthesized. These included 25 kinds of orcilaldehyde derivatives, 8 kinds of β-orcilaladehyde derivatives, 7 kinds of atranol derivatives, and 22 kinds of divaraldehyde derivatives. Antibacterial action of these compounds were tested with human type tubercle bacilli, the sensitive H37RvS strain and the resistat H37RvR strain which is resistant to over 300 μg/ml of streptomycin, 50 μg/ml of p-aminosalicylic acid, and 50 μg/ml of INAH. None of the compounds tested had antibacterial action against these two strains.
Tachyphylaxis to the effects of 2-(2-diethylaminoethyl)-1-phenylisothiuronium bromide hydrobromide (DEPT), one of the 2-aminoethylisothiuronium (AET) derivatives, has been studied on the blood pressure of anesthetized rat and spinal cat, and also on the nictitating membrane of the cat. The pressor responese to DEPT declined gradually with successive injections ; the extent of tachyphylaxis induced by DEPT depended on the dosage and on the frequency of injections. But a complete depression could not be observed after 25 injections with this compound. The tachyphylaxis induced by DEPT is not crossed to tyramine or amphetamine, and is not recovered with noradrenaline infusion. Tachyphylaxis induced by tyramine in normal animals is recovered with noradrenaline infusion, but is not recovered with noradrenaline infusion after treatment with nialamide, a drug which inhibits monoamine oxidase, or large does of DEPT. In animals treated with nialamide, the tachyphylaxis induced by DEPT was similar to that in normal animals, but the tachyphylaxis to tyramine was induced more rapidly after treatment with nialamide and was similar to that produced by amphetamine in normal animals. These results mentioned above indicated that the tachyphylaxis mechanism of DEPT might be different from that of tyramine or amphetamine. Effects of reserpine, cocaine, guanethidine, bretylium, hexamethonium and tetraethylammonium to the pressor response of DEPT in urethane anesthetized rat were also investigated.
A new glycoside (I), C24H26O18·11/2H2O, mp 274-275°, was isolated from Chrysosplenium grayanum MAXIM. (Japanese name"Nekonomeso"), and a glycoside (II), C24H26O12·2H2O, mp 175-176°, from C. flagelliferum FR. SCHM. (Japanese name"Tsurunekonomeso"). I was determined as oxyayanin-A (5, 2', 5'-trihydroxy-3, 7, 4'-trimethoxyflavone)-2'-glucoside, and was named chrysosplenoside-A, and II as pendulin (5, 4'-dihydroxy-3, 6, 7-trimethoxyflavone-4'-glucoside).
A new colorimetric method for microdetermination of isothiocyanates was established, using 3, 6-dinitrophthalic acid as a color developing agent in a potassium carbonatesodium thiosulfate solution. The reaction conditions were examined with allyl isothiocyanate as a model compound. The outline of the procedure is as follows : To 2.0 ml of allyl isothiocyanate solution (10-150 μg/ml), (dissolved in 50% ethylene glycol solution, 1.0 ml of 3, 6-dinitrophthalic acid monopyridinium salt solution (0.1%), and 1.0 ml of alkaline solution (40% potassium carbonate and 30% sodium thiosulfate) are added and mixed well. The mixture is heated in a boiling water bath for exactly 10 minutes, cooled in running water, and diluted to 20.0 ml with water. The absorbance of the developed color is read at 400 mμ against the reagent blank. In this color reaction, 3, 6-dinitrophthalic acid was assumed to be reduced to 3-amino-6-nitrophthalic acid by S2-, which was liberated from allyl isothiocyanate in the alkaline medium.
2-(p-Aminophenyl)-5-bromo-4-methyloxazole (XIII) and 4-bromo-, 4-iodo-5-methyl-2-sulfanilamidoisoxazole (VII, XVII) were synthesized by direct bromination or iodination of 2-(p-acetamidophenyl)-4-methyloxazole (XII) and 5-methyl-3-(N4-acetylsulfanilamido) isoxazole (XIV), followed by deacetylation, in good yield.
Ecdysterone (I) and inokosterone (II) were isolated and identified from the terrestrial portion of Achyranthes fauriei, whole herb of A. japonica, root of A. bidentata (crude drug of Chinese origin) and its Japanese cultivated species (Hitachi Goshitsu), root of Formosan A. rubrofusca, and whole herb of Formosan A. longifolia. Only I was isolated from the terrestrial portion of Formosan A. obtusifolia and whole herb of Formosan Cyathula Prostrata.
For the purpose of establishing the absolute configuration of enmein (I) by chemical means, (-)-6-methyl-7-oxobicyclo [3. 2. 1] octane (VIII) was prepared by a sequence of reactions shown in Chart 3 and 5. The synthesized compound was found to be an enantiomer of the compound (XXXIII) obtained by pyrolysis of disdehydrodihydroenmein. Since the absolute configuration of VIII is deduced from that of the intermediate (XXIIIb), the absolute configuration of the pyrolysis product (XXXIII) has been clarified. The result thus obtained is in agreement with the absolute configuration of enmein proposed in in the previous paper.
In the reaction of dimethyl sulfoxide with 2-furyl bromomethyl ketone (Ia), 5-nitro-2-furyl bromomethyl ketone (Ib), and 4-bromophenacyl bromide (Ic) at room temperature, methyl 2-furoylthiol formate (IIIa), methyl 5-nitro-2-furoylthiol formate (IIIb), and methyl 4-bromobenzoylthiol formate (IIIc) were newly isolated besides 2-furylglyoxal (IIa), 5-nitro-2-furylglyoxal (IIb), and 4-bromophenylglyoxal (IIc). Variation in the amounts of IIa, b, c and IIIa, b, c formed was examined by gas chromatography while varying the reaction temperature and time.
A new glycoside, mp 248-251°, was obtained from the leaves of Staphylea Bumalda DC. (Japanese name'Mitsuba-Utsugi'). This substance gave a dark purple color to ferric chloride reaction, was negative to the flavone reaction, and the presence of a carbonyl group and a conjugated double bond was presumed from its infrared spectrum. Hydrolysis with 10% sulfuric acid afforded 2 moles of glucose and an aglycone as pale yellow prisms, mp 269-270°, which formed a diacetate of mp 134-136°. The NMR spectrum of the aglycone suggested it to be 2-methyl-5, 7-dihydroxychromone (noreugenin), and the fact was confirmed by mixed fusion and comparison of the infrared spectra with the synthesized sample. It follows, therefore, that this glycoside is noreugenin 7-diglucoside and was named staphylin.
From the acetonation product of riboflavin, several new O-isopropylidene derivatives of riboflavin were isolated. Periodate oxidation of mono-O-isopropylidene derivatives and riboflavin dibenzoates derived from mono-O-isopropylidene compounds showed that the structures of these O-isopropylidene derivatives are 2' : 4', 3' : 5'-di-O-isopropylideneriboflavin (II), 4' : 5'-O-isopropylideneriboflavin (III), 3' : 4'-O-isopropylideneriboflavin (IV), and 2' : 3'-O-isopropylideneriboflavin (V). Partial hydrolysis of II and 2' : 3', 4' : 5'-di-O-isopropylideneriboflavin (I) afforded 2' : 4'-O-isopropylideneriboflavin (VI) and V respectively.
Gas phase dehydration of isoamylalcohol on spherical alumina catalyst was studied by a packed bed reactor. The reaction was operated under the constant conditions of 350°and the atmospheric pressure. The main products were 3-methyl-1-butene, 2-methyl-1-butene, 2-methyl-2-butene and water, and we could neglect the other byproducts for our calculation. The reverse process of dehydration reaction might be neglected. By the analysis of our results (Fig 3, 4), this dehydration reaction was summarised as equations (7)-(12), and we determined the rate-constants from our results.
Syntheses of cis- and trans-10-amino-11-hydroxy-10, 11-dihydrodibenzo [b, f] thiepin and their derivatives are described. Their steric configurations are clarified by using desulfurization reaction with Raney nickel.
Coriose (D-altro-3-heptulose) (I), sedoheptulose (II), methyl α-D-galactoside (III) and myo-inositol (V) were isolated from the methanol extract of red fruit of Coriaria japonica after removing tutin by extraction with chloroform, and also glucose and fructose etc. by fermentation, treating with ion-exchange resins, and then passing through a charcoal-Celite column. Volemitol (IV), I and V were isolated from seed of red fruit. The mother liquor of coriamyrtin extract from leaf and stems gave I and V. The presence of these constituents in the plant has been confirmed by paper partition chromatography of the juice pressed from fresh fruit and stem, and also by gas liquid chromatography of trimethylsilyl ether. Distribution of the other sugar constituents was also investigated.
N-oxidation of 1-methyl-(I) and 1-benzyl-phthalazine (II) was attempted at lower than 10° in the mixed solvents of chloroform and ether using monoperphthalic acid. 2-Oxide (I2) and 3-oxide (I3) were produced from I in a 1 : 2 ratio and from II 2-oxide (II2) and 3-Oxide (II3) in almost a 3 : 1 ratio. The position of N-oxide groups were determined by the following procedures. To I2 and I3, phenylmagnesium bromide was reacted respectively and the reaction solution was treated with p-benzoquinone to 2-oxide (III2) and 3-oxide (III3) of 1-methyl-4-phenylphthalazine (III). III2 was confirmed by the synthesis separately carried out in reacting 1-phenylphthalazine 3-oxide (IV3) with methylmagnesium iodide. Therefore, the structure of I2 was decided and that of I3 might be suggested. Similar procedures were made in the determination of the structures of II2 and II3. It was reported that only 2-oxide (III2) was produced from 1-methyl-4-phenylphthalazine (III) and that from 1-isopropyl-4-phenylphthalazine (VII), only 3-oxide (VII3) was produced (Chart 3). N-oxidation of 1-ethyl-4-phenylphthalazine (IX) was attempted and only 2-oxide (IX2) was obtained (Chart 4).
Crossed extensor reflexes of the leg were elicited by stimulation of the contralateral n. fibularis in the anesthetized and in the spinal chickens. Dose-response curves of several central muscle relaxants and of some central nervous system stimulants were obtained. Mephenesin and meprobamate depressed the reflex in the non-spinal chicks in the same degree as in the spinal ones, suggesting that the spinal cord was the main site of action of these drugs. Diazepam, chlordiazepoxide and carisoprodol depressed the reflex stronger in the non-spinal chicks than in the spinal chicks, probably because these drugs affected the brain as well as the spinal cord. Strychnine and picrotoxin showed characteristic stimulating effects. The antagonistic pattern of the relaxants against strychnine was different from that against picrotoxin. From these results it was confirmed that the crossed extensor reflex in the young chicks could be available for the investigation of the central muscle relaxants.
In a previous paper, we studied the extraction mechanism of caffeine from crushed tealeaf and determined the mass transfer coefficients of diffusional, capillary and washing extractions. In this paper, tropine alkaloid is extracted from slices of Scopoliae Rhizoma cut to various sizes in water and buffer (pH 4, 5, 6). In this case, capillary extraction does not take a part, because extraction rate is independent on agitation. Then, extraction takes place by washing and diffusion mechanisms. We determine the mass transfer coefficient of these two mechanisms by analysis of the extraction rate, which depends distinctly on pH of the solvent (Table III).
A new glycoside (I), C25H28O13·2H2O, mp 226-228°, [α]20D-30° (c=0.2, pyridine) was isolated from Chrysosplenium tosaense MAKINO (Japanese name"Tachinekonomeso"). I was assumed to be 5, 4'-dihydroxy-3, 6, 7, 3'-tetramethoxyflavone 4'-monoglucoside and was named chrysosplenoside-B.
Pharmacological properties of 2-aminoethyl-1-p-chlorophenylisothiuronium bromide hydrobromide (AEPCIT), one of the 2-aminoethylisothiuronium (AET) derivatives, were examined and compared with those of 2-aminoethyl-1-phenylisothiuronium bromide hydrobromide (AEPhT). AEPCIT possessed slightly stronger adrenergic α-blocking action and local anesthetic, antispasmodic actions than AEPhT. While AEPCIT showed the marked negative inotropic action on isolated heart of guinea pig, the positive inotropic and chronotropic actions were observed on the vagotomized open chest dog. Acute toxicity was also tested.
Two flavonoid glucosides were isolated from the stems and leaves of Agrimonia pilosa LEDEBOUR var. japonica NAKAI (Rosaceae), which did not yet bear any flower, by 6-Nylon column chromatography and were identified as luteolin 7-β-D-glucoside and apigenin 7-β-D-glucoside by mixed fusion and IR spectra. Its whole herb is in general called Ryugeso.
By the ether extraction of the syrupy portion from the methanol extract of Poncirus trifoliata RAFINESQUE, four kinds of compound such as seselin (mp 119-120°), marmesin (mp 185-186°) and β-sitosterol (mp 136-137°), as well as γ-sitosterol have been isolated in crystalline state for the first time from the plant.