Fluorescence ability was examined With the reaction mixture of 2,3-naphthalene-dicarboxaldehyde and aromatic primary amines. In a strongly acid medium. the solution was found to exhibit fluorescence reaction different from that of previously reported o-phthalaldehyde or 4,5-methylenedioxyphthalaldehyde. By the utilizgtion of this fluorescence reaction fluorometric determination of aromatic primary amines with 2,3-naph-thalenedicarboxaldehyde was established. Sensitivity of this method is approximately equal to that using 4,5-methylenedioxyphthalaldehyde. It was found from fluorescence characteristics of 2-(p-sulfamoylphenyl)-benz[f]isoindoline-1,3-diol and of the reaction mixture that this fluorescent substance is 2-phenylbenz[f]isoindoline-1,3-diol, and it Was assumed that the fluorescence in a strongly acid medium is due to ite halochromism.
π-Electron density of 2-phenylphthalimidine and its derivatives was calculated by the simp1e linear combination of atomic orbitals (LCAO) molecular orbital method and its relation to fluorescence was examined. In 2-phenylphthalimidines, contribution of ionic resonance structure increases in excited state than in ground state. For 2-phenylphthal-imidines to produce fluorescence, π-electron distribution must incline towards the phenyl group from phthalimidine nucleus in transition from the ground state to excited state. If this inclination is reverse or when such inclination is absent, the compound does not show any fluorescence. The calculated value of the wave length obtained from the energy difference between first excited state and ground state in π-system was in parallel with the observed values of the maximum wave length of fluorescence of 2-phenylphthalimidines was due to π*-π transition.
It has been found that sulpyrine is produced from a mixture of 4-methylaminoanti-pyrine and sodium hydroxymethanesulfonate even in aqueous solution. On the other hand, a part of sulpyrine is hydrolyzed in aqueous solution into 4-methylaminoantipyrine and sodium hydroxymethanesulfonate as a result of dissociation. Thin-layer chromato-graphic studies revealed that the dissociation product of sulpyrine in aqueous solution is 4-methylaminoantipyrine, and that 4-aminoantipyrine, 4-formylmethylaminoantipyrine, iminobisantipyrine, and 4, 4'-[methylenebis(methylimoino)]diantipyrine are scarcely produced in ordinary condition. As both of the dissociation products were found not to undergo further decomposition or irreversible reaction, quantitative relations among sulpyrine, 4-methylaminoantipyrine, and hydroxymethanesulfonate were investigated by their separatory determination using ion-exchanger resin Dowex 1 x 4 (Cl). Results of these investigations indicate that sulpyrine exists in an equilibrium with 4-methylamino-antipyrine and hydroxymethanesulfonate. Equilibrium constants were measured at some temperatures and different pH solutions, and the effect of pH and temperature on equilibrium constant us discussed. Enthalpy of the dissociation reaction of sulpyrine in aqueous solution was calculated as -7.3 kcal./mole and the equilibrium constant K was related to the absolute temperature T by the formula, log K=1.60.x103/T-2.560.
In 1964, Taplin, et al., 1) and Wagner, et al.2) developed a new radio pharmaceutical, macro-aggregated albumin labeled with iodine-131 (131I-MAA), and successfully used this material as the tracer for pulmonary scanning in man. However, their method of preparating 131I-MAA was not always satisfactory from the point of isotope yield and quality for selective pulmonary scanning. Various processes for preparation of MAA regarding isotope yield, and quality for pulmonary scanning were examined and the following series of preparation was concluded to be the best. Human serum albumin is labeled with 131I, pH is adjusting to 5.5 by buffer solution, and after sterilization, it is poured into a vial. Then this solution is heated in a boiling water bath for 20 minutes with vigorous shaking and cooled to room temperature. This is centrifuged for several minutes at 2000 -2500 r.p.m., the supernatant material is removed, and the sediment is resuspended in the buffer solution of pH 5.5.
The formyl group of glyoxylate is hydrated, and metal chelate formation between the carbonyl group and the hydrated formyl group was investigated hrough IR spectra, pH measurements, etc. The molar ratio of glyoxylic acid to metal was 1 to 1 in Cu(II), Ni(II), Co(II), and Mn(II) chelates. Marked drop in pH was found on reaction with Cu(II), Al(III), or Fe(III) ion (Table I); Stretching vibration of C-O in the hydrated formyl group near 1090 cm-1 was split by cbelation (Figs. 4 and 5, and Table II), and the deformating vibration of O-H near I300 cm-1 shifted to a higher wave numbef by chelation. Asymmetric stretching vibration of the carboxylate group is almost the same as 1604 cm-1 or lower in Cu, Ni, Co, and Mn chelates, Therefore, M-O bonding in glyoxylic acid chelates of Cu and other metals is recognized as ionic. M-O bonding of Fe and Al is, however, coordinative, because Vas(coo) of these chelates is shifted to a higher wave number.
Reaction of D-glucaro-1, 4-lactone (I) and -6, 3-lactone (II) with ammonia and alkyl-amines afforded a monoamide (XII and V), N-alkyl-D-glucaro-1-amide 6, 3-lactone (XIV) and N-alkyl-D-glucaro-6-amide 1-acid (IX). XIV and IX formed D-glucaric acid N, N-dialkylamide (X) by a disproportionation-like reaction but XII and V underwent hydrolysis into a monoammonium salt (VI) of D-glucaric acid by the same reaction.
Xanthosine was directly phosphorylated in 63.9% yield by using a mixture of 2-cyano-ethyl phosphate and dicyclohexylcarbodiimide (DCC). The linear gradient elution by ion-exchange chromatography showed that the phosphorylated products contained xanthosine 5'-phosphate, xanthosine 2'(or 3')-phosphate, and xanthosine 2'(or 3'), 5'-diphosphate in 40.3, 29.4, and 27.6%, respectively.
In continuation of the work reported in the previous paper, in order to elucidate the radiochemica1 reaction mechanism of liquid organic compounds from their electric conduction phenomenon in the γ-field, effect of voltage and temperature on electric resistance when sealed in liquid paraffin was examined by using a special measuring cell having a wide electrode area. It was found that electric resistance increased with increasing voltage, contrary to the time of non-irradiation. Effect of temperature on electric resistance is smaller during irradiation than without irradiation, and the activation energy calculated from the observed value was about 0.2 eV by irradiation of 1.2x105 r./hr. against about 0.7 eV without irradiation. This indicates that activation energy falls at the time of irradiation, same as in solid polymers. Dose-rate response was fast, being below 30 seconds, and was within the transition rate of the radiation source or sample in the laboratory. The values at the time of re-irradiation reproduce the values corresponding to the irradiation dose. From these results, it is considered that the majority of electric couduction during γ-irradiation is due to electrons.
Iron colloid for intravenous injection was successfully prepared by the use of sodium chondroitinsulfate as the stabilizer. In order to examine the nature of this. colloid, comparative examinations were made with iron colloids using other kind of stabilizers. Liberation of ferric ion from various kinds of iron colloid in aqueous solution of various pH was examined, and the behavior of iron in the body was followed by intravenous injection of iron colloid labelled with 59Fe, in rabbits. A certain correlation was found between these in vitro and in vivo experiments.
It was e1ucidated that 2-(o-aminophenylthio)-3, 5-dichloropyridine (III), 4-(o-aminophenylthio)-3-nitropyridine (VIII), and their acyl (formyl, acetyl) derivatives undergo rearrangement to the corresponding disulfides (V and IX) by catalytic action of alkyl halide as well as ethanolic hydrogen chloride. On the basis of the spectroscopic data and experimental results, the mechanism of this rearrangement was discussed.
In connection with the synthesis of A and B rings for the preparation of streptonigrin (I) and II, hexachlorobenzene was derived to 1, 2, 4-trichlorobenzene (IV), which was dinitrated to VII, and 7-ammo-5-chloro-6, 8-dimethoxyquinoline (XIV)-and 7-amino-5, 6, 8-trichloroquinoline (XI) were obtained. For the preparation of XIV, VII was derived to VIII, methoxylated to XII, reduced to the diamino compound (XIII), and finally derived to XIV by the Skraup reaction For the preparation of XI, VII was reduced directly to X which was submitted to the Skraup reaction. Both XIV and XI resisted methoxylation and XV, corresponding to the A-B portion of II, could not be obtained.
Nitration of 2-phenylquinoline 1-oxide (I) gives a 4-nitro compound. Reaction of 2-phenylquinoline 1-oxide (I), 4-phenylquinoline 1-oxide (XI), and 2, 4-diphenylquinoline 1-oxide (XVI) with acylating agents was examined under various conditions. The reaction of XI all progressed towards formation of 2-substituted compounds. On the other hand, reaction of I sometimes furnished 4-substituted compounds (III, IV, VI, VIII) and sometimes 3-, 6-, and 8-acyloxyl compounds (V, IX, X). Reaction of XVI invariably produced 3-, 6-, and 8-hydroxy derivatives. Considerations were made on the mechanism of this reaction.
The structure of 4-oxo-3, 4-dihydro-2-quinazolinepropionitrile (I), which had been presumed from its infrared and ultraviolet spectra, 1) was established by the following sequence of reactions. Hydrolysis of I afforded 4-oxo-3, 4-dihydroquinazoline-2-propionic acid (II), which was found to be identical with the substance obtained by palladium-carbon reduction of 4-oxo-3, 4-dihydro-2-quinazolinacrylic acid (VII) prepared from 2-methyl-4(3H)-quinazolinone (V). This fact proves that I is 4-oxo-3, 4-dihydro-2-quinazolinepropionitrile. Attempts to obtain II directly by the reaction of anthranilic acid and 3-cyanopro-pionamide failed to materialize and the product was found to be 2, 2'-ethylenedi-4(3H)-quinazolinone.
In order to examine the nature of acetyl group bonded directly to the isoquinoline ring, 3, 4-dihydrolsoquinolines (V) and 1, 2, 3, 4-tetrahydroisoquinolines (VI) were prepared from vanillin by the usual method. Condensation of these compounds with ethyl acetate, in the presence of sodium hydride, and ketonolysis of their products unexpectedly afforded the dehydrogenated 1-methyl-3-acetyl-6, 7-dimethoxyisoquinoline (X) instead of IX, from V. In the case of VI compounds, majority of them produced X and formation of XII was not detected. In order to prove the formation of X, V was dehydrogenated to XIII and submitted to ketonolysis through XIV under the same conditions as above. The product X thereby obtained showed no depression of the melting point when fused with the foregoing product.
Following the isolation of biscoclaurine alkaloids, isoliensinine (I) and neferine (II), from Lien-Tze-Hsin (embryo of Nelumbo nucifera GAERTN.) from a Hong Kong market, further examinations were made on this crude drug and nuciferine (IV) and pronuciferine (V) were isolated from the non-phenolic portion, and lotusine (VI) from the water-soluble quaternary base portion. Examination of lotus seeds from commercial markets in Kathmandu, Nepal, revealed the presence of neferine (II) and liensinine (III) (cf. Table I).
An infrared spectrophotometric procedure was used for simultaneous determination of small amounts of sumithion and methylparathion in a mixture extracted from spinach and lettuce. Measurements of the strong absorption peaks at 10.3μfor sumithion and at 10.8μ for methylparathion permit the determination of about 1 p.p.m. of these insecticides with 50 g. of spinach or lettuce.