By a method similar to that reported in Part I of this series, catalytic reduction of benzenediazonium chloride, after coupling, over palladium-carbon afforded 2, 7-dihydroxy-3-amino-8-methylchromone hydrochloride in a similarly good yield. The alkenylhydroxybenzoic acid, described in Part II of this series, and chromancarboxylic and 2, 3-dihydrobenzofurancarboxylic acid, obtained by its cyclization, were derived to respective acid chloride and reacted with the above chromone compound in pyridine to obtained 3-acylamino-4-hydroxycoumarins, having structure analogous to novobiocic acid.

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From the compound considered to be 4-hydroxycoumarin in the past, tautomeric 4-hydroxycoumarin and 2-hydroxychromone were each isolated. With their infrared spectral characteristics as the standard, tautomers of 4-hydroxycoumarin derivatives were distinguished. 4-Hydroxycoumarin derivatives all possess coumarin structure in dioxane, indicating that this state is more fundamental than the chromone structure, which is present in associated state in the solid. It is therefore proposed that these compounds be named by the 4-hydroxycoumarin structure in the state of solution in dioxane.

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7-Hydroxy-4-iminohydrocoumarin was reacted with ethylene chlorohydrin and α-monochlorohydrin in dimethylformamide, in the presence of sodium methoxide to form 7-(2-hydroxyethoxy) and 7-(2, 3-dihydroxypropoxy) compounds, which were hydrolyzed with 50% sulfuric acid to 4-hydroxycoumarin derivatives, and coupled with benzenediazonium chloride to form the phenylhydrazone compound. Catalytic reduction of this compound over palladium-carbon finally gave 7-(2-hydroxyethoxy) or 7-(2, 3-dihydroxypropoxy) derivatives of 3-amino-4-hydroxycoumarin as their hydrochlorides. The reaction of this hydrochloride in pyridine with 2, 2-dimethyl-6-chromancarbonyl chloride or 3-(3-methyl-2-butenyl)-4-acetoxybenzoyl chloride gave demethylcyclo-novobiocic acid and demethylmonoacetylnovobiocic acid as ethyleneglycolide or glyceride. Further reaction of these with diethylcarbamoyl chloride in pyridine gave the corresponding diethylcarbamoylglycolide or diethylcarbamoylglyceride. The glyceride of demethylmonoacetylnovobiocic acid was reacted with ethyl chloroformate in pyridine to form 2-hydroxy-3-ethoxycarbonyloxypropoxy compound and standing of its solution in ammoniacal methanol afforded the carbamoylglyceride of demethylmonoacetylnovobiocic acid.

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Application of tetra-O-acetyl-D-glucopyranosyl bromide to 3-acetamido-4, 7-dihydroxycoumarin and cyclonovobiocic acid in hydrous acetone, in the presence of sodium hydroxide, afforded tetra-O-acetyl-D-glucopyranoside which was deacetylated in sodium methoxide to form D-glucopyranoside. Heating of 3-acetamido-7-(tetra-O-acetyl-D-glucopyranosyloxy)-4-hydroxycoumarin in acetic anhydride effected cyclization to form 7-(tetra-O-acetyl-D-glucopyranosyloxy)-2-methyl-4H-[1] benzopyran-[3, 4-d]oxazol-4-one and this proved that the glucosidic linkage is at 7-position.

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Catalytic reduction of 7α-hydroxydiosgenin (I), 7α-hydroxycholesterol (VIIIa), and 7α-methoxycholesterol (VIIIb) over platinum produces the corresponding 5β and 5α compounds and the 7α-hydroxyl group is invariably liberated by hydrogenolysis.
Hydrogenation of the double bond at 4 in 7α-(tetrahydro-2-pyranyloxy)cholest-4-en-3-one (XI) over palladium, followed by removal of the pyran ring affords 7α-hydroxy-5β-cholestan-3-one (XIIb), whose oxidation gives 3, 7-diketone (XIII). Huang-Minlon reduction of (XIII) produces 5β-cholestane (XIV). The Huang-Minlon reduction of the ketol (XIIb) gives 5β-cholestan-7α-ol (XVa), whose oxidation gives 5β-cholestan-7-one (XVI). Reduction of this ketone with sodium borohydride reverts it to the 7α-ol (XVa) and the reduction with sodium and isopropanol produces 7β-ol (XVIIa).

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Numerous reports have appeared on the determination of epirenamine and dl-norepirenamine. In order to establish a practicable colorimetric method of determination, examinations were made on various methods and it was found that colorimetric determination is possible by coloration with dimethyl-p-phenylenediamine as the reagent to effect indophenol reaction, extraction of the colored substance with isobutanol, and measurement of the optical density of the extract solution, this giving only a slight error. Examinations were also made on separatory determination of epirenamine and dl-norepirenamine, and epirenamine and phenylephrine. This separatory determination was found to be possible by the use of paper partition chromatography by the one-dimensional, ascending method, using a mixture of benzyl alcoholacetic acid-water (5:2:5) for epirenamine and dl-norepirenamine, and a mixture of butanol-acetic acid-water (5:2:5) for epirenamine and phenylephrine as the developing solvent.

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2-(Isonicotinoylhydrazono)propionic acid is a tridentate ligand possessing three donor groups and formed metal chelates with bivalent or trivalent metal ion in 2:1 ratio. These chelates were isolated and their properties were examined. A chelate having the composition of calcium bis[2-(isonicotinoylhydrazono)propionate] calcium (II) and this chelate was considered to be the stable enol type chelate.

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When 2-(isonicotinoylhydrazono)propionic acid, as a bidentate ligand, coordinates with metal ion with coordination number of 6, there is a possibility of the presence of coordinated water molecule. Therefore, measurement was carried out on the coordination compounds with the central atom having the coordination number of 4 and 6, using thermal balance and X-ray technique, and it was assumed that this is a simple water of crystallization.
The calcium (II) chelate comes in three kinds of crystal form, orthorhombic, triclinic, and spherulite. The orthorhombic crystal possesses seven molecules of water of crystallization and the otherr two forms, which are polymorphic, possess six moles of crystal water.

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It was found that the ultraviolet spectrum of isonicotinic acid hydrazide in alkaline solution showed the appearance of a strong absorption band at 297mμ, assumed to be due to the contribution of an enol type, and the same tendency was found in 2-(isonicotinoylhydrazono)propionic acid calcium (II) chelate. This was assumed to be due to enolization of the carbonyl which coordinates to form a complex radical with bivalent negative charge. The presence of an absorption band at 303mμ in the calcium (II) chelate supports the above view.
The absence of absorption band for N-H stretching vibration in the region of 3000cm^-1 and N-H deformation band at around 1300cm^-1 in the infrared spectrum of enol-type chelate also supports the presence of an enol-type chelate. The presence of these absorption bands proved the presence of a keto-type chelate.

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Following the previously reported work on the condensation rate of sulfa drugs and sodium glucuronate in a solvent of acetone-water system, examinations were made in the present series of work on the condensation rate of these two substances in nonaqueous solvent system. The present method was able to give, more easily and in a better yield than the existing method, N-glucuronides of sulfa drugs and aromatic primary amines with small Kb. Dimethylformamide was used as the solvent for sulfa drugs and ethylene glycol or glycerol for sodium glucuronate. The two solutions were mixed and addition of acetic acid as the reaction catalyst gave the objective N-glucuronade. This method is thought to be of value in examination of metabolic products of sulfanilamide preparations and other aromatic primary amines and for preparation of water-soluble derivatives of these compounds.

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N-Glucuronides of various sulfonamides are now obtained in a good yield and in high purity by the method developed by Ôgiya and Hashimoto. Concerning the fact that these N-glucuronides are soluble in water and that decrease in toxicity over the parent sulfonamide may be expected, growth inhibition of Escherichia coli by these N-glucuronides was tested in vitro. In the present series of experiments, comparative examinations were made on the growth inhibition of the N-glucuronides of sulfapyridine, sulfathiazole, sulfanilamide, and sulfadiazine in the same concentration, using each sulfa drug alone or an equimolar mixture of the sulfonamide and sodium glucuronate. It was thereby found that growth-inhibitory action is markedly weak but this inhibitive action increased according to the degree of liberation of the sulfonamide by decomposition under suitable conditions of pH and sterilization of the culture solution. This point was clarified by comparison of the decomposition rate of N-glucuronide.

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It was discovered that salicylamide can be used as an amination agent. Condensation of salicylamide with 4-chloroquinaldine compounds results in the formation of compounds of N-(2-methyl-4-quinolyl)salicylamide and 4-aminoquinaldine types, differing from the case of m- and p-hydroxybenzamides, the hydroxyl being stabilized by intramolecular chelation and the acid amide acting like an amine. On the other hand, condensation of m- and p-hydroxybenzamide with 4-chloroquinaldine compounds results in hydroxyl substitution and compound of 4-(carbamoylphenoxy)quinaldine type is formed.

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Synthesis of 4-hydroxyphenoxyquinaldine series compound was carried out with 4-chloroquinaldine series compounds and dihydroxybenzene, and it was found that three kinds of product were formed from this reaction, viz. ether-type condensate (III) of 2 moles of 4-chloroquinaldine compound and 1 mole of dihydroxybenzene, ether-type condensate (IV) of 1 mole of 4-chloroquinaldine compound and 1 mole of dihydroxy-benzene, and a compound (V) formed by dehydrochlorination-cyclization of (IV).
The reaction of resorcinol with 3-(2-chloroethyl)-4-chloroquinaldine (Ia) and 2-methyl-3-(2-chloroethyl)-4-chloro-8-quinolinol (Ib) results in formation of the compounds of (III) and (IV) types. The reaction of pyrocatechol with (Ia) produces (III) and (V) type compounds, with a small amount of (IV) type compound. In the reaction of pyrocatechol with (Ib), the compound of (IV) type is comparatively stable, and the product is a mixture of (III), (IV), and (V) type compounds. Reaction of hydroquinone with (Ia) is the same as that with pyrocatechol, and compounds of (III), (IV) and (V) type are formed, while the compounds of (III) and (IV) types are formed from (Ib).

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Condensation of aminophenol with 4-chloroquinaldine compounds chiefly results in condensation at the amino group but condensation at the hydroxyl partly occurs in compounds possessing a chloroethyl group with -I effect at the 3-position of the quinoline ring. Condensation of o- or p-aminophenol with 3-(2-chloroethyl)-4-chloro-quinaldine gives 1-(2- or 4-hydroxyphenyl)-4-methyl-2, 3-dihydro-1H pyrrolo[3, 2-c]quinoline (I) accompanied by a small amount of a compound (II) formed by dehydro-chlorination-cyclization of 3-(2-chloroethyl)-4-(2- or 4-aminophenoxy)quinaldine. The compound of the (I) type alone was formed in the condensation with m-aminophenol. Condensation of o-, m-, or p-aminophenol with 3-vinyl-4-chloroquinaldine resulted in the formation of 3-vinyl-4-hydroxyanilinoquinaldine alone.

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It was found that an enzyme which effects hydrolysis of steroidal ester was present in malt enzyme (Diastase J. P. or its original powder), Taka-diastase, and pig pancreas diastase. This hydrolase hydrolyzes the acetoxyl in 16, 17, 20, and 21 position but not that in other positions, indicating a rather interesting selectivity. This hydrolysis occurs when the aqueous solution of foregoing enzyme preparation is added to ethanolic solution of steroidal ester and the mixture allowed to stand over night. This method was utilized for the hydrolysis of monohydroxylated Reichstein's substance S diacetates (Ia to Id) and the corresponding monoacetates (IIa to IId) were obtained in a good yield.

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Hydrolysis of steroidal ester by malt enzyme shows selectivity, not only to the position of the ester but also to difference in the acyl group. Such selectivity could be summarized as follows:
1) Ester group in the 21-position which submit to hydrolysis are the esters of straight-chain aliphatic carboxylic acid, lower dibasic aliphatic carboxylic acid, and N-substituted amino acid.
2) Ester group in the 21-position which does not submit to hydrolysis are esters of aromatic carboxylic acid, dibasic aliphatic carboxylic acid with a large number of carbon atoms, carbonic acid, and tertiary carboxylic acid.
3) Of the esters of secondary hydroxyl in 17-position, formate and acetate are hydrolyzed but not propionate.
4) Formate and acetate in 3-position are not hydrolyzed.

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Examinations were made on enzymatic properties and reaction conditions for hydrolysis of steroidal esters by malt enzyme and following facts were revealed: (1) Optimal pH is ca. 6.5. (2) Suitable reaction temperature is in the range of 10-30°. (3) Best solvent for the substrate solution is methanol, followed by ethanol. (4) Relationship between enzyme and substrate concentration and reaction time was clarified. (5) The use of diastase (J.P. VI) as the enzyme preparation eliminates adjustment of pH since the enzyme preparation itself has pH-buffering action, and the procedure becomes easier.

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The acetoxyl group in 21-position of steroids is easily hydrolyzed by malt enzyme but not those in 11- and 19-positions. This selectivity was utilized for formation of 11α, 17α-dihydroxyprogesterone (VI) from 11α-hydroxylated Reichstein's substance S (I) by the route shown in Chart 1, and of 17α, 19-dihydroxyprogesterone (XIII) and 17α-hydroxy-19-norprogesterone (XV) from 19-hydroxylated Reichstein's substance S (VIII) by the route shown in Chart 2.

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Hydrolysis by malt enzyme shows selectivity, as reported earlier, and this reaction is characterized by its progress under a very mild condition. This characteristic was utilized for the preparation of acid- and alkali-labile 16β-hydroxylated Reichstein's substance S (IV) and its 16-acetate (III), from its 16, 21-diacetate. (IV) undergoes rapid isomerization to 16α-hydroxylated substance S (V). Oxidation of (III) with sodium bismuthate gives 16β-acetoxyandrost-4-ene-3, 17-dione (VI) whose treatment with sulfuric acid or potassium hydroxide produces 16-oxotestosterone (VII).

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Following the previously reported work on the measurement of specific gravity and dielectric constant of propylene glycol-water system of various concentrations, the dipole moment of the same system was calculated. The dipole moment was calculated by the use of Ishidate-Kamura formula for propylene glycol in associated state from the concentration-dielectric constant curve of a propylene glycol-water mixture and changes in equivalue dipole moment were observed at around 50% and 90% of propylene glycol, the values of dipole moment being 4.04×10^-18 e. s. u. for 0-50%(w/w) of propylene glycol, 3.85×10^-18 e. s. u. for 50-85%, and 3.81×10^-18 e. s. u. for 85-100% of propylene glycol.
The foregoing method was used to calculate the dipole moment of aqueous solution of glucose and the values obtained were 8.18×10^-18 e. s. u. for 0-10%(w/w) and 5.96×10^-18 e. s. u. for 20-50%(w/w). This result revealed that aqueous solution of glucose begins to differ in association state at around 10%. The dielectric constant of aqueous glucose solution decreases with passage of time and reaches a constant value after about 24 hours.

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In continuation of previous works, pharmacological action of N-isopropyl-1, 5-dimethylhexylamine hydrochloride (No. 4) was examined. The bronchodilating activity of this amine tested by excised lung infusion is approximately the same as that of ephedrine against ACh and histamine and about 1/10 that of epirenamine. The compound effected contraction of excised blood vessel but antagonized contraction by epirenamine to cause dilation, while it narrowed vascular diameter (in frog tongue) in approximately the same degree as that of ephedrine. Lowering of capillary permeability tested by various method showed the amine to possess somewhat greater activity than ephedrine and diphenhydramine, and more powerful than flavonoids or carbazochrome series pharmaceutics. The compound had almost no effect against methylhexabital sleep in mice and its anesthetic effect on cornea surface of a guinea pig was weaker than that of procaine. The compound was also found to have hemostatic effect comparable to ephedrine.

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In continuation of previous work, pharmacological action of N-alkyl-1, 5-dimethylhexylamine derivatives was examined. The compounds of this series showed no great difference in their action on blood pressure and antispasmodic effect, all the compounds effecting lowering of blood pressure, but their activities were comparable to or weaker than that of diphenhydramine. Structure-activity relationship indicated the great significance of N-alkylation, as in the case of aralkylamines. In antispasmodic effect, the compounds were comparable to ephedrine in both anti-acetylcholine and anti-histamine activities, and the effect of N-alkylation was not so marked as on blood pressure. The compounds showed various degree of activity in the lowering of capillary peameability and iso-type compounds with 3-5 carbon atoms alone were effective. Hypotensive action of N-isopropylated compound (No. 4) is generally inhibited by cardiotonic drugs but, differing from isoproterenol, this action was not inhibited by dichlorisoproterenol, or rather it was fortified. This compound (No. 4) was slightly antagonistic to atropine and was antagonistic in both acetylcholine and histamine.

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Pharmacological activity, especially systemic action and experimental therapeutic effect, of N-isopropyl-1, 5-dimethylhexylamine hydrochloride (No. 4) was examined. This amine had no effect on the erythrocyte and blood platelet counts in a rat but the eosinophile count showed significant decrease. The compound also gave no change of rectal temperature in a rabbit. It was inert to oxidative deamination by monoamine oxidase or rather, it showed stronger antagonistic inhibition than ephedrine. Spirometer experiment with a dog by Konzett's method showed the compound to have a bronchodilating action and the compound was effective against experimental asthma induced by histamine or acetylcholine. In a forced swimming experiment using mice, the compound showed prolongation of swimming time, similar to that of AC-17.

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In order to find the action mechanism of N-isopropyl-1, 5-dimethylhexylamine hydrochloride (No. 4 or Metron) against excised smooth muscle, interaction of this compound and known pharmaceutics was compared by concentration-action curve. In excised seminal vesicle of a guinea pig, Metron itself had no effect but it antagonised the contraction by epirenamine. In excised trachea of a guinea pig, the compound showed contraction and relacting according to its concentration, same as ephedrine and methoxyphenamine. Contraction by Metron was not antagonized by atropine but relacting was antagonized by dichlorisoproterenol. Antagonistic action of Metron against acetylcholine showed additive synergetic effect by the combination with epirenamine, diphenhydramine, papaverine, etc. Both the contraction and relaction effects of Metron did not show techyphylaxis.

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A series of ethyl 2-aminomethyl-3, 3-di(2-thienyl)acrylates were prepared. These compounds were planned to agree with general rule for analgesics and to possess combined characteristics of dithienylaminobutene compounds and pethidine hydrochloride. However, their analgesic and antitussive actions were not as strong as were expected but were stronger than that of ethyl 2-aminomethyl-3, 3-diphenylacrylates.

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The derivatives of ethyl N-(2-tert-aminoalkyl) carbanilates and N-(2-tert-aminoalkyl) ethanesulfonanilides were prepared. These compounds were planned to agree with general rules for analgesics and to have a tertiary nitrogen with one less phenyl group in place of the quaternary carbon in the analgesic skeleton. Pharmacological action of these compounds will be reported elsewhere.

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In connection with the antibacterial action of antibiotics possessing cyclic hydroxamic acid-type atom group, attempts were made to prepare 4-thiazolidinone derivative having this characteristic atom group in the molecule. In order to prepare 3-hydroxy-4-thiazolidinones, potassium thiocyanate was reacted with N-hydroxy-2-chloroacetamide or N-benzyloxy-2-chloroacetamide to form 2-imino-3-hydroxy-4-thiazolidinone (I) or 2-imino-3-benzyloxy-4-thiazolidinone (II). However, instead of the condensation at 3-position, the anticipated substituent underwent rearrangement to the 2-position and 2-hydroxyimino-4-thiazolidinone (III) was obtained from the N-hydroxy compound and 2-benzyloxyimino-4-thiazolidinone (IV) from the N-benzyloxy compound. On the other hand, cyclization of ethyl monochloroacetate and 1-phenyl-3-hydroxy-2-thiourea or 1-phenyl-3-benzyloxy-2-thiourea failed to afford compounds with hydroxyl or benzyloxyl in the 3-position, these substituents being found in the 2-position to form 2-hydroxyimino- (VI) or 2-benzyloxyimino-3-phenyl-4-thiazolidinone (VII). It was concluded from these experimental results that the hydroxyl and benzyloxyl groups are more stable in the 2-position and undergo rearrangement to that position.

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Several kinds of antibiotics have been found which possess atomic group of cyclic hydroxamic acid type. It was considered that chelate formation of hydroxamic acid took part in the appearance of antibacterial action in these antibiotics and derivatives of 2-methyl-4(3H)-quinazolinone, 2, 4(1H, 3H)-quinazolinedione, and 2-phenyl-4-benzylidene-2-imidazolin-5-one with such atom group in the 3-position were prepared. Some of their related compounds were also prepared in which the hydrogen atom in the hydroxyl of hydroxamic acid had been substituted with benzyl or the hydroxy substituted with hydrogen, methyl, phenyl, or amino group to lose the ability as a chelating reagent. Antibacterial activity of these compounds was tested against tubercle bacilli but clear-cut conclusion was not obtained with a group of these compounds.

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Good result can be obtained in photometric titration of potassium iodide in hydro-chioric acid solution by the addition of ethanol and titration with potassium periodate at 290mμ, thereby preventing volatilization of iodine produced. In accordance with this result, potassium iodide and iodine solution are accurately measured, titrated in sulfuric acidity with 0.001M potassium periodate (a cc.), the same amount of the two substances are measured accurately, and titrated with 0.001M potassium periodate in hydrochloric acidity (b cc.), by which a cc. would correspond to the amount of I^- and b-5/2a cc. to I₂. This method is advantageous in that a minute amount of I₂ and I^- can be determined by the same oxidation agent.

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A new process for synthesis of L-glutamine via N-formyl-L-glutamine was discovered. It was proved that the deformylation is effected not only by mineral acid but also by hydrazine hydrate. The same was found to be true with N-formylated peptide.

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Infrared absorptions in the region of 700-1000cm^-1 were examined in 16 kinds of 1, 3-cyclohexanedione derivatives. Of the three absorptions bands in 1, 3-cyclohexanedione (I) of ν₁ at 1212, ν₂ at 1180, and ν₃ at 1141cm^-1, the band corresponding to ν₃ is lacking in the 4-substituted compound, while that in the 5-substituted compound shifts to a higher wave-number and overlaps with the ν₁ band. Assignments listed in Table II were made from the behaviour of these bands to deuteration.
The intensity of these bands decreases in 2-carbonylated compounds and a few bands of strong intensity appeared in its stead in the region of 1000-1100cm^-1.

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A part of the micro-amount components of natural honey was thought to originate in the component of occluded pollens and the present series of experiments was carried out as a part of studies on pollens. Chemistry of pollens has increased interest from pure chemical and pharmaceutical standpoint and the components detected are numerous. However, analytical work in this country is small due probably to the difficulty in collecting pollens. Analyses have been made on limited number of pollens, mostly on those in the honey collected by bees and on those especially of interest from allergic considerations.
Microchemical examinations were made on the flavonoids, whose physiological action is of interest in medicopharmacological field, among the many kinds of pigment contained in pollen grains, in their distribution and properties with 17 genera (37 kinds) of anemophilous plants and 51 genera (95 kinds) of entomophilous plants. Presence of carotenoids was found less in the pollens of anemophilous plants and more in the entomophilous plants, and the pollens which contain a large amount of carotenoids have less flavonoids. Many of the anemophilous plants contain isorhamnetin but not in entomophilous plants. Quercetin, one of the most widely distributed flavonoids in nature, is also found in numerous pollens. Past workers indicated that only one kind of a flavonoid is found in the pollens of one flower but the present series of experiments have shown that two or three kinds of flavonoid are present in one kind of a pollen. It was also found that pollens of some plants have different kind of flavonoids in the wild and horticultural species.

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3-(3-Methyl-2-butenyl)-4-hydroxybenzoic acid, a constituent component of novobiocic acid, and the cyclized product of a structurally related allyl-hydroxybenzoic acid, chromancarboxylic acid, and 2-methyl-2, 3-dihydrobenzofurancarboxylic acid, were prepared. Antibacterial activity of these alkenylhydroxybenzoic acids and their derivatives was examined and the ethyl ester of 3-(3-methyl-2-butenyl)-4-hydroxybenzoic acid and 3-allyl-4-hydroxybenzoic acid showed antibacterial activity. For comparison with alkyl p-hydroxybenzoates, which are used as antiseptics, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, allyl, hydroxyethyl, and dihydroxypropyl esters of these acids were prepared. Their amides were also prepared to examine their relationship with novobiocic acid.

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The procedure of the Friedel-Crafts acylation of acetanilide was simplified and the yield raised by preliminary heating of acetanilide and aluminium trichloride, cooling of this mixture, and addition of aryl chloride. Exchange of N-aryl groups occured in benzoylation and 36% of the product was found to be 4′-benzoylbenzanilide. Separation of two products was easily effected by the difference in the rate of their hydrolysis.
Nitration of the 4′-acylacetanilide formed by this reaction was extremely facile and the yield was good in benzophenone derivatives but that of the others failed with mixed acids. This was very difficult even with other reagents, the yield of the purified product being around 20% when using nitric acid and acetic anhydride, and around 40% when using copper nitrate and acetic anhydride.

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Anodic synthesis was carried out with the hitherto unknown ester, methyl hydrogen 3-methyl-3-ethylglutarate, as the starting material. Electrolysis of the mixed salt of this acid ester and monobasic acid in methanol afforded some branched-chain fatty acids of the general formula R-CH₂-C(CH₃)(C₂H₅)-CH₂COOH (with R=CH₃, C₇H₁₅, C₉H₁₉, C₁₁H₂₃, and C₁₅H₃₁), either in free state or as a derivative. As the symmetrical coupling product of the ester, dimethyl 3, 6-dimethyl-3, 6-diethylsuberate and 3, 6-dimethyl-3, 6-diethylsuberic acid were obtained. Apart from the branched-chain fatty acids, mixed electrolysis of phenylacetic acid and methyl hydrogen succinate was carried out in methanol and 4-phenylbutyric acid was obtained in a low yield. This is one example of an anodic synthesis of this kind of aromatic carboxylic acid.

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Ether extract of the rhizome of Heracleum lanatum var. asiaticum HARA, growing wild in the Hokkaido, afforded five kinds of furocoumarins, isobergapten, bergapten, isopimpinellin, and pimpinellin which were identified through physical constants, mixed fusion, and preparation of derivatives. The extract also yielded β-sitosterol. The ethanolic extract of the fruit of this plant also afforded bergapten and imperatorin. The latter was identified with xanthotoxin and 3-methyl-2-buten-1-ol. The ethanolic fraction was submitted to gas chromatography with the synthetic products, and identity was established.

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