Stabilities of 3-morpholinosydnonimine (II), hydrochloride (I) and N-ethoxycarbonyl-3-morpholinosydnonimine (VIII) were examined by photometry, potentiometry, thin-layer chromatography and spectroscopy. In alkaline solution VIII goes to ethanol, carbon dioxide and II, which successively decomposes to N-morpholino-N-nitrosoaminoacetic acid (V) and N-cyanomethylenaminomorpholine (VI) via N-morpholino-N-nitrosoaminoacetonitrile (III). In the processes of I=II=III, the initial equilibrium is very rapid and the consecutive cleavage is a spontaneous first order reaction at pH 3-7 or a base catalyzed reaction at pH 8-10. The initial process of is a base catalyzed. first order hydrolysis of N-ethoxycarbonyl group. Hydrolyses of I and VII in hydrochloric acid form morpholine, nitrogen, chloroacetic acid and ammonium chloride. Photolyses of I and VII in acid solution at γ<320mμt give glycolic acid beside the products mentioned above. Formation of I from III and hydrolysis of VI to N-aminomorpholine are acid catalyzed pseudo-first-order reactions. Decomposition of III to VI seems to be a radical reaction.

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In order to discuss the property of selenium as a ligand atom and the effect of the substituent to complex formation in the related compounds of selenocysteamine, γ-aminopropylselenol, α-dimethyl-β-aminoethy selenol, α-methyl-β-aminoethylselenol, N-ethylaminoethylselenol and N, N'-dimethylaminoethylselenol were synthesized. Acid dissociation constants were determined by potentiometric titration and the values were compared with those of sulfur analogues. Stability constants of their metal complexes were calculated.

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For the model solution of the parenteral formulation, four ternary solutions were used: NaCl-KCl-H₂0 with 10% of total solutes, NaCl-mannitol-H₂0, NaCl-glycine-H₂0 and mannitol-sorbitol-H₂0 with 5%.
Measurements were carried out on the electrical resistance and the temperature of the sample solution during cooling and rewarming, and the change of the macroscopic appearance of the frozen sample during freeze drying was observed.
The eutectic temperature T_e and the collapse temperature T_e of the solute matrix were derived from above measurements and observation.
The mechanism of the collapse during freeze drying was discussed in relation to the state of frozen sample and T_e was classified in three types: the first was related to T_e, the second to a glass transition temperature T_e and the third was the temperature below which the gross matrix of crystallized solute persisted even in the presence of a small amount of solution among crystallized solutes and ice crystals.
From the properties of supercooled aqueous solution, it was found that the solution which did not exhibit eutectic crystallization could be freeze-dried if the temperature of sample was controlled below T_e. It was also suggested that the difficulty of freeze drying of the solution with low T_e could be improved by addition of a suitable solute.

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The chemical structure of chikusetsusaponin V, C⁴⁸H₇₆O₁₉ 2H₂O, mp 240-241°, [x] ²²_D+2.85°(Me0H), a main saponin isolated from the rhizome of Panax japonicum was established to be β-D-glucopyranosyl oleanate-(3)-Β-D-glucopyranosyl-(1→2)-β-D-glucuronopyranoside as represented by formula (1).

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Irradiation of 6-chloro-3 (2H) pyridazones (I), maleic hydrazides (IV), and 3, 6-dichloropyridazines (V and VI) in methanol containing HC1, afforded γ-lactones, methyl paraconates (II), and dimethyl succinates (III).
A shot time irradiation of 3, 6-dichloropyridazines (V) resulted in the formation of methylated pyridazines (VI and VII), hydroxymethylated pyridazines (VIII), and methylated pyridazones (IX), along with the γ-lactones (II) and the succinates (III).
The mechanism of the formation of the γ-lactones and the succinates was also discussed.

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Two new glucosides, which have been elucidated to be 1-O-β-D-glucopyranosyl-scylloinositol (Ia) and 1-O-β-D-glucopyranosyl-proto-quercitol (IIa), were isolated from an aqueous extract of the leaves and branches of Quercus stenophylla MAKINO (Japanese name “Urajirogashi” )
Besides these we detected other disaccharides by gas-liquid chromatography (Fig.)

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The formation of lipohydroperoxide from polyunsaturated fatty acid was accelerated by the addition of 12-keto oleic acid (12-KOA) in the state of oil-in-water system. Saturated or hydroxy analogues failed to show such prooxidant action.
Increasing concentration of added 12-KOA was found to promote the rate of peroxidation.
The acceleration of peroxidation is not affected by either the esterification of 12-KOA or the preincubation of keto acid with albumin.
Taking the fact that 12-KOA is easily absorbable through intestine contrary to lessabsorbability of lipohydroperoxide into consideration, it is suggested that keto acid produced in edible oil will act as potent prooxidant in vivo.

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Decomposition reaction of 2α, 5-epoxy-5α-cholestan-3-one tosylhydrazone (1b) and the 17β-acetoxyandrostane analogue (1d) with lithium hydride in toluene or xylene yielded the corresponding 1β, 3β-cyclo-2α, 5α-epoxy derivatives (2a and 2h) comprising a 3-Oxatricyclo [2.2.1.0^{2, 6}] heptane system. The structure of 2a, assumed from its spectral properties, was evidenced by the results of its catalytic hydrogenation providing the reductive cleavage products of the C₁-C₃ and the C₂-C₃ bond.

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A nucleophilic addition of phenol to N-(2-pyridylmethylene) aniline (I) is described. Electron density around carbon atom ortho to phenolic hydroxyl group and acidity of phenol are the two factors governing the outcome of the reaction. The effects of structural variation of Schiff base on its reactivity are also discussed. Extension of the reaction involved addition of 8-hydroxyquinoline to the Schiff base (I).

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3Β, 17α-Dihydroxy-5α, 14β-pregnan-20-one (III) and 3β-hydroxy-5α, 14β-pregn-16-en-20-one (VII) were prepared from 14β-isoandrosterone (I) by way of the 17β-ethynyl-17α-hydroxy derivative (II) in satisfactory yield. The reactivities of the nucleophilic reagents such as potassium cyanide, thioacetic acid, ethylenimine and nitromethane toward the Δ16-20-ketone system in VII have been investigated. All these nucleophiles showed the β-side attack yielding the 16β-substituted derivatives, in which the configuration of the side chain at C-17 was α. These results may be ascribable to the characteristic feature of C/D-ring fusion forming the cage-like structure.

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Alkaline hydrolysis of pharbitin, a purgative resin glycoside of the seeds of Pharbitis Nil C_HOISY (Convolvulaceae) gave a glycosidic acid “pharbitic acid” together with (+)-χ-methylbutyric and nilic ((-)-α-methyl-β-hydroxybutyric) acids as reported by Asahina, and in addition, valeric and tiglic acids. Tetrahydroxydecanoic acid which was reported by Kromer to exist in the organic acid fraction was not obtained and it is presumed to be a mixture of (-)-α-methyl-β-hydroxybutyric acid and (-)-α-methyl-β-O-(α-methyl-β-hydroxybutyroyl)-butyric acid, an artefact formed from the former. On acid hydrolysis of “pharbitic acid, ” ipurolic (3, 11-dihydroxytetradecanoic) acid was yielded accompanied by a very small amount of convolvulinolic (11-hydroxytetradecanoic) acid, and as the sugar portion, besides D-glucose and L-rhamnose, D-quinovose was provided.

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Trans-1-Amino-1, 2, 3, 4-tetrahydro-2-(3-methoxyphenyl) naphthalene (IV) was synthesized by the reduction of oxime (VIII). Mannichr eaction of IV with formalin and acetaldehydea ffordedb enz [c] phenanthridines, XI and XII, respectively. The amine (IV) was treated with pyridineh ydrochloridteo givep henolic base (V). Thec ondensation, of V with carbonylc ompoundws asi nvestigatedto givet he corresponding benz [c] phenanthridine derivatives (XV-XX). In the case of benzaldehydec, yclizationw asf ound to occur at both positions, para and ortho to the hydroxylg roup to give XVII, XVIII, and XX. Furthermorea, cetylationo f these phenolic benz [c] phenanthridines and an alternative synthesis of XII were also described.

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On photolysis of anisol or phenol with chloroacetamide, methoxy-or hydroxyacetamides were easily obtained. This reaction is one of alkylation on aromatic ring with alkyl halide in very mild condition and provides an example of photo-induced Friedel-Crafts reaction. A photorearrangement of phenoxyacetamide to hydroxyphenylacetamides in good yield was observed. Some discussion for mechanisms of these reactions were also described.

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A new method of extraction, i. e. electrodialytic extraction was proposed. Electrodialytic extraction apparatus was also devised. Extraction conditions were examined and the following results were obtained.
1. Electrodialytic extraction was more effective than shaking extraction.
2. Possibility of electrodialytic extraction of a test component could be demonstrated by using a liquid sample.
3. Acetic acid (0.5_M) was chosen as the acidic standard carrier solution.
4. A suitable current density was 20mA/cm² when using this apparatus and 0.5_Macetic acid as the carrier solution.
5. It is desirable for the carrier solution to be a weak electrolyte with specific conductivity of about 1×10^-3mho/cm.
6. Change in quantity of sample required no essential prolongation of extraction time.
7. The suitable particle size of the sample was about 100 mesh.
8. Cellulose membrane was chosen as the dialysis membrane for extracting low molecular compounds.

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Tetrahydrofolic acid exhibited a life-prolonging effect in the midlethally X-irradiated mice, when it was intraperitoneally injected in the animals after the irradiation. In the tetrahydrofolic acid-treated animals, retardation of the growth rate in the body weight was normalized in 5 days after the irradiation. Recovery in spleen and intestine weights as well as in the number of circulating blood leucocytes was more pronounced in the tetrahydrofolic acid-treated animals than in the control animals. However, it failed to increase the survival rate of the X-irradiated HeLa S₃ cells, when it was added in the culture medium after the irradiation.
In a subsequent experiment, it was clarified that folic acid was devoid of this therapeutic effect.

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DL-trans-and DL-cis-2-(1-Phenylcyclohexyl) cyclohexylamine (trans- and cis-II) were prepared from _DL-2-(1-phenylcyclohexyl) cyclohexanone (I) and submitted to deamination reaction with HNO₂, expecting steric government of 1-phenylcyclohexyl group as an extraordinarily bulky substituent. As a result, steric effect was observed more remarkably in the reaction of trans-II than of cis-II. On the way to completion of the reaction, cis-II nitrite was isolated as one of unusual examples. In addition, dehydration reaction of trans- and cis-alcohol derived from I and the Chugaev reaction of their xanthates were undertaken to prepare reference compounds for the identifications of products from the deamination reaction. All reactions involved in this study were mechanistically discussed.

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1) The structure of theasapogenol E, one of seeds sapogenols of Thea sinensis L. has been established as 3β, 16α, 21β, 22α, 28-pentahydroxy-23-oxo-olean-12-ene (III). In conjunction with the study on alcoholic alkaline treatment of theasapogenol E leading the isomerization and/or the Meerwein-Ponndorf type reduction of the aldehyde function of III, it has been suggested that camelliagenin D (X) might be an artefact sapogenol. 2) The other two minor seeds sapogenols designated as theasapogenols D and C have been revealed identical with dihydropriverogenin A (=camelliagenin A)(IV) and camelliagenin C (V) respectively. Furthermore, the evidence supporting 22α-hydroxy (equatorial) of dihydropriverogenin A (IV) has been presented, which has led the revision of the previous structures of dihydropriverogenin A (e), priverogenin A (h) and priverogenin B (i). 3) On the basis of NMR examination, the conformation of some acetonide derivatives of dihydropriverogenin A (IV), barringtogenol C (I), and theasapogenol A (II) has been discussed.

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1) The sapogenol composition of Japanese horsechestnuts (Aesculus turbinata B_LUME, Hippocastanaceae) has been clarified asbarringtogenol C (1), aescigenin (VI), protoaescigenin (VII) and 16-desoxy-barringtogenol C (IX). 2) The structure elucidation of the new sapogenol named 16-desoxy-barringtogenol C (IX) has been described in detail. 3) The full account on the configuration of hydroxyl functions in ring E of aescigenin (VI; 22α-OH), protoaescigenin (VII; 21β-0H, 22α-OH) and isoaescigenin (VIII; 21α-OH, 22α-OH) in relation to barringtogenol C (I) and theasapogenol A (II) has been presented.

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An acidic polysaccharide has been isolated from the seed of Plantago major L. var. asiatica D_ECAISNE. The polysaccharide, named plantasan, was homogenous on gel chromatography and glass-fiber paper electrophoresis, and it was the representative mucilage of the seed. The component carbohydrates of it were _D-xylose, _L-arabinose, D-galacturonic acid, L-rhamnose and D-galactose, and the molar ratio of them was 15 : 3 : 4 : 2 : O. 4.

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Par condensation de cetones α-halogénés sur la dihydrorésorcine, nous avons syn-thàtisà les furocyclanones suivantes méthyl-2, -(1a), diméthy1-2, 3-(Ib), méthyl-3-(Ic) et phényl-2-(Id) oxo-4 tétrahydro-4, 5, 6, 7 benzofurannes. La structure de Id, composé non encore decrit jusqu'ici, a étéétablie à partir des spectres de RMN, des spectres infrarouges et de quelques propriétés chimiques. Les furocyclanones Ia et Id peuvent être condensées sur l'isatate de potassium ou sur l'acide anthranilique pour donner des dérivés originaux de la dihydro-4, 5 furo [2, 3-c] acridine, tandis que les furocyclanones Ib et Ic ne conduisent pas aux dérivés furoacridiniques attendus.

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The transguanylation of N-alklated derivatives of AET was followed at 15°with the potentiometric titration method. The reactivity was reduced markedly by the substi tution at the nitrogen atom of isothiuronium group. The rate was related closely with pK₂ (isothiuronium group) but not with pK₁ (ammonium group), which indicated that the proton releasing from isothiuronium group may be a limiting factor for the transguanylation. The rate increase was observed limitedly by the substitution at the nitrogen of ammonium group.

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An investigation was made on the reaction between o-phthalaldehydic acid (II) and various primary amino compounds.
The reaction with aromatic amines afforded 3-atylaminophthalides (IIIa-j) in good yield. However, the reaction with aliphatic amines did not afford expected III type compounds, but 3, 3'-(N-alkylimino) diphthalides (VIa-d). Similar type compounds (XIa-e) were prepared from ureas, acetamide, and ethyl carbamate.
3-Chlorophthalide (V) reacted with aniline to afford IIIa, but with aliphatic amines, 3-hydroxy-N-alkylphthalimidines (I Xa-d).

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For the purpose of improving the fluidity of solids for tabletting, various aqueous slurries containing synthetic aluminium silicate or magnesium carbonate and several kinds of binderes were spray dried using a centrifugal wheel atomizer. Gum arabic, gelatin, poly vinyl alcohol, carboxymethylcellulose, methylcellulose, and poly (vinylpyrolidone) were used as the binders. The finely agglomerated powders (10-80μ) obtained by this process showed free flowing properties and could be easily tablated, as opposed to the original powders. The surface of these products were examined by scanning electron microscopy. Important informations were obtained pertaining to surface topography. The geometric mean diameter (Do) of the agglomerated powder was found to be influenced primarily by the type of binder used and its concentration. Some physicochemical properties of the agglomerated powder, i.e., fluidity and packing, were also examined and the most important factors influencing these properties were found to be particle size and specific surface area.

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Lithiation of ring-methoxylated N, N-dimethylnaphthalenemethylamines was investigated. The lithiation of 4-methoxy-2-naphthalenemethylamine types (XV and XVII) resulted in a setective lithiation on position 3, teading to an efficient method of β, β'-bis-carbon-substitution on the naphthalene or anthracene ring system. As an application, new syntheses of 1-oxygenated 2, 3-naphthalides (XXXII, XXXIII, XXXV, and XXXVI) or 5-oxygenated 2, 3-naphthatides (XLII) were accomptished via carboxylation of lithio derivatives, quarternarization of the resulting amino Qcids and subsequent pyrolysis.

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Theanine (N-ethylglutamine), a flavourous constituent of tea leaves, was studied in respect of the influence on the central nervous system in mice.
Theanine was shown to inhibit the convulsive action of caffeine, but was ineffective against pentetrazole, picrotoxin, strychnine, pipradrol and bemegride as well as L-glutamine. Neither theanine nor L-glutamine effected on the prolongation of the sleeping time after the injection of hexobarbital sodium in mice. Using ¹⁴C-labeled theanine, it was found that the intraperitoneally administered theanine was taken up by brain tissue with out undergoing the metabolic changes in a 30minutes. The intracerebral level of γaminobutyric acid was shown to increase significantly at 30minutes following the intraperitoneal administration of theanine in mice.

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It has been reported that N-(α-methylbenzyl) linoleamide (MBLA) had a remarkable cholesterol-lowering effect on the experimental hypercholesterolemia in rabbits and rats.
There are three optical isomers of MBLA: D-, L- and DL-MBLA because of an asymmetric carbon atom in the amine moiety of MBLA. And the potency of the cholesterol-lowering effect was found to be the following order: D->DL->L-MBLA.
Fukushima also found that the respiratory excretion of ¹⁴C after oral administration of carboxy ¹⁴C-labeled L-MBLA to rats was significantly greater than that of D- or DL-MBLA, whereas the ratio of urinary ¹⁴C excretion of D-MBLA was higher than that of L- or DL-MBLA. These results suggest that the difference of the cholesterol-lowering potency observed among the MBLA isomers might be closely related with the difference of biological disposition of the isomers.
The present paper describes the results of in vitro studies on the enzymatic hydrolysis of the amide linkage of MBLA isomers.

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In general, acid dye is known to react with amine or quarternary ammonium salt to form a colored compound. Bromothymol blue, bromocresol greens or bromophenol blues has been used for the conventional determination of thiamine, quartenary ammonium compound or quinine.
Tetrabromophenolphthalein ethyl ester (TBPE) is well known as a pH indicator. Various amines and organic cations were found to be extracted with TBPE into 1, 2-dichloroethane. The colors of the extracted species can be classified into the following three categories.(1) Blue species which is extracted by the presence of acrinol base, sparteine or thiamine.(2) Red-violet species which is developed by the presence of N, N-dimethylpiperazine, eserine or triethanolamine.(3) Yellow species which is the same color as reagent blank even in the presence of aniline, 3-aminoquinoline, pyridine, N, N-dimethylformamide, EDTA, or NTA. The discussion of this paper deals with a spectrophotometric determination of acrinol base by solvent extraction with TBPE. The proposed method has a better reproducibility and a higher sensitivity. The titrimetric method has been used for the determination of acrinol which is widely used as disinfectant. 3-Methyl-2-benzothiazolinone hydrazone-ferric chloride was described as a spectrophotometric reagent for acrinol.

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