The Clauson-Kaas-type microhydrogenating apparatus is constructed of a reaction chamber and a compensator of equal volume, connected by a manometer and the whole apparatus is immersed in a thermostatic bath, so that a very stable motion may be expected. Actually, however, it requires one hour or more for the manometer scale to reach equilibrium after sweeping of the reaction chamber with hydrogen. This phenomenon is more marked, the higher the vapor pressure of solvent and the higher the temperature of thermostatic bath. This is caused by the asymmetric construction of the reaction chamber and compensator, the latter being so much simpler in construction than the former and consequently the internal space of the compensator rapidly reaching stabilized vapor pressure of the solvent. This means that the compensator is not playing the role it was designed for, i.e. compensation of pressure variation inside the reaction chamber. It was therefore concluded that hydrogen should be bubbled through the solvent before its introduction into the apparatus, by which the manometer will reach equilibrium rapidly, and that there was no significance in immersing the compensator in a thermostatic bath. It was also concluded that the volume of reaction chamber should be minimized to effect stabilization of pressure and that the apparatus should be redesigned to facilitate diffusion of solvent vapor.
An improved microhydrogenating apparatus was devised by removing the compensator from Clauson-Kaas' apparatus and minimizing the volume of reaction chamber. By the use of this apparatus, even with the use of ethanol with comparatively high vapor pressure, stabilization of pressure is obtained 20-30 minutes after sweeping with hydrogen. On the other hand, calculation of analytical result by the formula proposed by Clauson-Kaas tends to give somewhat negative value. On examination of this point, it was found that this formula is a theoretical one based on ideal condition in which hydrogen is completely saturated with the solvent vapor and this is far from the actual state. It was observed that hydrogen in the reaction chamber is not saturated with the solvent vapor even one hour after sweeping with hydrogen and in this case, the amount of mercury added and consumption of hydrogen become equal. It was thereby concluded that the correction of solvent vapor pressure in the Clauson-Kaas' calculation formula is unnecessary. This correction becomes more marked as the solvent vapor pressure and thermostat temperature become higher, ethanol at 30° giving about 10% error in analytical results and still higher 20% error at 40°.
Mutual solubility of nicotine-water-salt system at 30° was determined, using potassium and sodium carbonate, sodium and ammonium sulfate, and potassium and sodium chloride as salts. It was thereby learned that the conjugation curve, if shown by molar fraction, becomes almost a straight line within a certain concentration range, and that there was a definite rule to dehydrative ability of salts, as had been found earlier. The order of these salts in dehydrating nicotine is rather irregular when compared to pyridine and 2-picoline and this must be due to the characteristics of nicotine.
N-(1-Methyl-2-thiocyano-4-hydroxy-1-butenyl)-N-[(2-methyl-4-amino-5-pyrimidinyl)-methyl] formamide (cyanothiamine) (I) is converted to N-[1-(2-thiacyclobutyliden)-ethyl]-N-[(2-methyl-4-amino-5-pyrimidinyl) methyl] formamide (II) on application of alkali to its aqueous solution. The presence of methanol in this reaction solvent results in concurrent formation of N-(1-methyl-2-methylthio-4-hydroxy-1-butenyl)-N-[(2-methyl-4-amino-5-pyrimidinyl) methyl] formamide (VII). These are all new specific reactions for 3-hydroxypropyl thiocyanate derivatives and is thought to go through intermediate products (XXI) and (XXII). Application of cyanogen bromide to 3-(2-methyl-4-amino-5-pyrimidinyl) methyl)-4-methyl-5-(1-hydroxyethyl) thiazolium salt (XIII) in alkaline state was found to result in direct formation of thiacyclopropylidene derivative (XXXVII) and thiocyano derivative (XLIII) was not isolated, as in the case of thiamine.
Dehydrogenation of C-alkylated piperazines by catalytic vapor-phase reaction afforded the corresponding alkylpyrazines. The catalysts used were zinc oxide-Fuller's earth and copper chromite-silica-alumina. The optimal temperature is 375-400°, but sufficient dehydrogenation was effected even at 325° in the case of piperazine, affording pyrazine in 33.4% yield. Dehydrogenation of 2-methyl-, 2, 3-dimethyl-, 2, 5-dimethyl-, and 2, 3, 5-trimethyl-piperazines gave the corresponding alkylpyrazines in 35-45% yield, while the dehydrogenation of 2, 3, 5, 6-tetramethylpiperazine proceeded more smoothly, affording the corresponding tetramethylpyrazine in 62.5% yield.
1) Heating of N-(2-hydroxyethyl)-1, 3-propylenediamine and N-methyl-N-(2-hydroxyethyl)-1, 3-propylenediamine in an autoclave, in the presence of a dehydration catalyst, afforded the seven-membered ring compounds, homopiperazine (yield, 11-15%) and N-methylhomopiperazine (yield, 13.3%), respectively. Dehydrative cyclization of N-(2-hydroxyethyl)-1, 3-propylenediamine by fusion of hydrohalide gave homopiperazine in 10.5-17% yield in the case of hydrochloride and 17-27.5% in the case of hydrobromide. In the case of N-alkyl-N-(2-hydroxyethyl)-1, 3-propylenediamine, the reaction was accompanied by liberation of the alkyl group and only homopiperazine was obtained. 2) Reaction of trimethylenediamine and ethylene glycol in dioxane, in the presence of Raney nickel, in an autoclave, afforded homopiperazine in 10% yield, except in the case of ethylenediamine and trimethylene glycol.
Examinations were made on five kinds of synthetic silica-alumina of different manufacturing process, acid clay, and acid-treated white clay as to their physical properties, such as molar ratio of silica to alumina, bulk density, density, surface area, mean granular diameter, pinhole volume, and mean pinhole diameter. The silica-alumina prepared by the coprecipitation method, formed in the high pH-range, possessed larger content of alumina, small surface area, and large average pinhole diameter, while the synthetic silica-alumina prepared by step-precipitation method and acid clay possessed smaller content of alumina, due to the effect of acid treatment, with greater surface area and smaller mean pinhole diameter. Surface acidity of synthetic silica-alumina was determined by the Tamele method to examine the correlationship between the reaction of aniline and methanol, and catalytic activity at the time of preparation of N-methylmorpholine from N-methyl-bis(2-hydroxyethyl) amine. It was thereby found that the acidity determined the ease or difficulty of liberation of the product from catalyst surface, the catalyst of higher acidity increasing the number of methyl groups introduced in the reaction of aniline and methanol, and increasing the rate of decomposition reaction during preparation of N-methylmorpholine.
3-Methylaminocamphor and 3-ethylaminocamphor were obtained in a good yield from 3-formamidocamphor. Application of haloacyl halides to 3-methyl- and 3-ethyl-aminocamphor afforded (N-methyl(or ethyl)-2-haloacylamino)camphors (VI to XIV) and these were converted to 3-[N-alkyl-2-dialkyl(allyl)amino(piperidyl)acylamino]-camphors (XV to XL) by condensation with dialkyl(allyl)amine and piperidine. The same reactions were carried out with 3-camphorylurea and 1-(2-haloacyl)-3-(3-camphoryl)ureas (XLI to XLIII), and 1-(2-dimethyl(or ethyl)aminoacyl)-3-(3-camphoryl)ureas (XLIV to XLIX) were obtained. 1-(2-Dialkylaminoacyl)-3-(3-camphoryl)-3-methyl(or ethyl)ureas were not isolated in crystalline form.
1) Reduction of the Schiff bases (II to VI) in alkaline ethanol, with palladium-charcoal or Raney nickel as a catalyst, afforded the corresponding 4-benzylamino-antipyrines (VII to XI) in good yields. 2) Compounds of general formula (E) were prepared in which n is 1 or 2, namely 4-(N-benzylbenzamido) antipyrine (XII), 4-(N-benzyl-2-dialkylaminoacylamido) antipyrines (XVII to XIX), 4-(2-dialkylaminophenylacetamido) antipyrines (XXIII to XXVI), 4-phenyl-acetamidoantipyrines (XXVII to XXIX) and 1-phenylacetyl-3-(4-antipyrinyl) urea (XXX), 4-(2-diallylaminoacylamido) antipyrines (XXXIV to XXXVI), and 4-(2-morpholinoacylamido)-antipyrines (XXXVII to XXXVIII).
1) It has been found that 1-(2-dimethylaminoacyl)-3-(4-antipyrinyl) urea derivatives, whose syntheses were described earlier, unexpectedly had low toxicity and a high safety margin. This is rather interesting considering that 4-antipyrinylurea is the final metabolite of aminopyrine. Therefore, compounds of this series, 4-antipyrinyl-thiourea derivatives (XIII to XXIX, XXXVIII, XXXIX) and 1-(4-antipyrinyl)-1-methylurea derivatives (XXXIII to XXXVII), were prepared. 2) Reaction of 4-aminoantipyrine (I) and CSCl2 affords 4-antipyrinyl isothiocyanate (II) while the reaction of (I) and COCl2 gives 1, 3-diantipyrinylurea (XXXI). Reaction of 4-methylaminoantipyrine (I′) and COCl2 affords N-4-antipyrinyl-N-methylcarbamoyl chloride (XXXII). Condensation of (II) and (XXXII) with various amines afforded the above-mentioned urea derivatives.
Infrared absorption spectra of 26 kinds of diphenyl ether derivatives, including dimethyldiphenyl, dinitrodiphenyl, and nitrochlorodiphenyl ethers, were measured in the region of 4000 to 660cm-1 and characteristic absorption bands for C-O-C bond were examined. There is a strong absorption band in the region of 1256-1238cm-1, considered to be due to asymmetric stretching vibration of C-O-C. Effect of nitro and chloro radicals on this absorption maximum is not so marked while the maximum is seen in a higher wave-number side in m-methyl substituents. As other characteristic bands, a medium absorption is observed in the region of 952-935cm-1 in diphenyl ether derivatives possessing a m-methyl or a m-nitro group, and in the region of 909-851cm-1 in other derivatives. Assignment of this absorption band is not clear but it may possibly be that of a symmetric stretching vibration of C-O-C. Examinations were also made on characteristic bands, other than the above, in the region of C-H out-of-plane vibrations.
Infrared absorption spectra of various dibenzo-p-dioxin derivatives were measured and a strong characteristic absorption band was found in the region of 1330-1280cm-1, considered to originate in asymmetric stretching vibration of C-O. At the same time, examinations were made on absorption bands for C-H out-of-plane vibration.
It had been found by Tomita that all substances containing the dibenzo-p-dioxin ring (III), whether synthesized or occurring naturally as trilobine-type alkaloids, without exception undergo blue or bluish green coloration with conc. sulfuric acid and conc. nitric acid, or by addition of potassium nitrate or other oxidation agents to their conc. sulfuric acid solution. This is known as the diphenylene dioxide reaction and this coloration is often used for characterization of compounds of this group. In 1957, however, Sandermann and others stated that the substance of the composition (C6OCl4)n, obtained by pyrolysis of pentachlorophenol (I), agrees with octachlorodibenzo-p-dioxin (II) and yet it is negative to the diphenylene dioxide reaction. Doubting the authenticity of this statement, Sandermann's substance (II) and several kinds of polyhalodibenzo-p-dioxins indicated in Table I were synthesized by the routes shown in Chart 1 and examinations were made on their general properties, coloration reaction, and infrared absorption spectra. It was thereby found that this coloration reaction is negative in the octachloro (II) and octabromo (VII) compounds, and in (XVI) and (XVIII), considered to be a polymer. The infrared spectra of the octachloro (II) and octabromo (VII) compounds show only extremely weak absorption in the region of 1280-1330cm-1, considered to be characteristic to the dibenzo-p-dioxin ring (cf. Fig. 1). It is clear, therefore, that the compounds (II) and (VII), which do not possess hydrogen atom in the dibenzo-p-dioxin ring, are negative to this coloration reaction in spite of the presence of this ring system. The two kinds of polymers, (XVI) and (XVIII), are considered from their infrared absorption spectra not to form the dibenzo-p-dioxin ring and are polymers of the diphenyl ether type, which justifies their negative reaction to this coloration.
Of the two antibiotics named Naramycin-A and -B, A was proved to be identical with cycloheximide and, in order to examine its biological properties, tests were made on its rodent repellency by the method of Traub and others. Naramycin-A derivatives, related substances, and the isomeric Naramycin-B were screened for rodent repellency by the tap-water acceptance method, and it was found that the acetate, benzoate, and dihydrocompound of Naramycin-A, and Naramycin-B itself had a marked effect. Naramycin-A, differing from rodenticides of coumarin series, had no activity of inhibiting blood coagulation, even by continuous dosage over three days in mice.
Adsorption of water vapor on compressed aluminum silicate was examined and tests were made to draw scanning adsorption isotherme inside the large hysteresis loop formed by adsorption and desorption isotherms. Continuous curve were successfully obtained with samples compressed at 0.76 and 1.5ton/cm2 and, therefore, calculations were made by the methods of Katz and Utsugi on the distribution of neck-radius and the volume of internal wide space which belongs to bottleneck type capillary. Results of calculations are presented in Tables I and II. data These shows that the capillary with narrow neck and the large internal volume has developed markedly.
Disintegration of aluminum silicate tablets differs greatly according to whether the tablets are dry or moist. The same is true of the amount of air that escapes when tablets are thrown into water. These data are presented in Table I. These two phenomena in moist tablets disappear when tablets are dried. The reason for these phenomena is the fine structure of the bottle-neck type capillary indicated in Table I in Part VII of this series. In such cases, condensed water closes the neck of capillary, even at a comparatively low equilibrium vapor pressure and stops immediate penetration of water even if internal space is void. Calculated from the data in Tables I and II (Part VII), liberation of air from the bottle-neck capillary decreases by 62.4% when the vapor pressure reaches equilibrium in the air of 60% relative humidity at 20°. This is approximately in accordance with the present experimental results shown in Table I of this report. The same may be said of water penetration. Sedimentation volume of disintegrated substance also differs according to whether the tablet is dry or moist. This is due to the difference in the state of layering in water by different amount of air liberated. Sedimentation volume is extremely large compared to tablet volume. Since the sedimentation volume is more stable than tablet volume in water, tablets in water will possess potential energy of disintegration.
Some pyrazolone derivatives are being used as the reagent for detection of metal ions but none of them are sensitive and specific. For the purpose of improving this situation, reaction of metal ions with heterocyclic pyrazolone derivatives, especially 1-(2-pyridyl)-3-methyl-5-pyrazolone and 1-(2-quinolyl)-3-methyl-5-pyrazolone, was examined and it was found that some ions show a marked coloration. The complex salts formed by these reagents and copper, nickel, manganese, and cobalt was found to be an intramolecular metal complex having the composition of 1 mole of the metal to 2 moles of the reagent.
In connection with the complex salt formed between metal ions and heterocyclic pyrazolone derivatives, reaction between metal ions and pyrazolone derivatives, in which a benzoyl group had been introduced into 4-position of the pyrazolone ring, was examined, since the pyrazolone derivatives tested to date lacked sensitivity and specificity. It was found that the metal complex salts formed in this case also had the composition of 1 mole of the metal to 2 moles of the reagent.
As new derivatives of phenylmorpholine having epinephrine-like activity, 2-(3, 4-dihydroxyphenyl)-N-methylmorpholine and 2-(3, 4-dimethoxyphenyl)-N-methylmorpholine were prepared. Isoquinoline-type cyclization of 2-(3, 4-dialkoxyphenyl) morpholine hydrochloride with formaldehyde afforded a new type 1H-2, 5-benzoxazine ring. Debenzylation of its dibenzyloxy compound by catalytic reduction over palladium-charcoal afforded 3, 4, 5, 6-tetrahydro-8, 9-dihydroxy-1, 5-methano-1H-2, 5-benzoxazine. Pharmacological tests revealed that some of these new derivatives possessed antitussive action better than that of codeine and 2-(3, 4-diacetoxyphenyl)-N-methylmorpholine seemed to be the most desirable of such compounds.
Various aconite alkaloids were successfully separated with the use of ion exchanger, Amberlite IRC-50, by stepwise elution with phosphate-acetate-borate buffer of different pH. It was thereby clarified that the adsorption of a base on this ion exchange resin was not in parallel with the pK value of the base and there is a certain amount of non-ionic adsorption.
A new glucoside, piceid, was isolated from the leaves of Picea Glehnii MASTERS. Oxidative decomposition of methylated compound of its hydrolyzate indicated that the aglycone of piceid is resveratrole. Since the oxidative decomposition of methylated piceid afforded anisic acid, it was found that glucose is bonded at 3-position of resveratrole (3, 5, 4'-trihydroxystilbene). From these facts and infrared and ultraviolet spectral data, the structure of piceid was proved to be represented by (III).
The basic substance in the venom of Formosan serpent, Trimeresurus mucrosquamatus CANTOR, was isolated as a picrate which crystallized from water as yellow needles, browning gradually at 238-239° and decomposing at 247-248° with effervescence. Its analytical values corresponded to those of spermine picrate, C10H26N4·4C6H3O7N3, and no depression of the decomposition point was observed on admixture. Its hydrochloride crystallized as needle or scaly crystals, gradually browning at above 280° and decomposing at 310-311°. Paper chromatogram of the hydrochloride gave the same Rf value as that of spermine hydrochloride while its paper electrophoresis (phosphate buffer of pH 6.1) showed the same rate of migration as that of spermine hydrochloride, moving to the cathode side. From these results, the basic substance in the Formosan serpent venom was determined as spermine. The content of spermine, calculated from the yield of its picrate is 6.6% of the dried venom or 2.1% of the fresh venom, calculated as the free base. The extremely high content of this substance should be worthy of note.
Formation ratio of thiolutin and aureothricin, the antibiotics produced by the Streptomyces sp., was shown to be determined by infrared absorption spectral analysis. Spectral measurements were made by the KBr-pellet method. The key bands are at 973 and 943cm-1. Determination of a standard mixed sample was effected with standard deviation of 1.6%. Some valuable observations were gained with regard to production mechanism of the Streptomyces sp.
The compounds of 4-methyl-2, 3-dihydrofuro[3, 2-c]quinoline (II) type are the intermediates formed during preparation of 3-(2-chloroethyl)-4-chloroquinaldine (III) by condensation of aromatic amine and 2-acetyl-γ-butyrolactone in the presence of phosphoryl chloride. When the reaction temperature is low, compounds of (II) type alone are formed while heating of (II) with phosphoryl chloride results in the cleavage of furan ring with concurrent chlorination to form (III). On heating (III) with acetic acid, the chlorine in 4-position is substituted with acetoxy and when this 4-acetoxy compound is heated with ethanolic 5% ammonia or sodium carbonate solution, acetic acid and hydrochloric acid are liberated to regenerate (II). Heating of (III) with benzaldehyde and acetic anhydride results in styrylation and formation of a furan ring to form 4-styryl-2, 3-dihydrofuro[3, 2-c]quinoline (IV).
Condensation of 2-naphthylamine and 2-acetyl-γ-butyrolactone by heating in the presence of phosphoryl chloride affords 1-chloro-2-(2-chloroethyl)-3-methylbenzo[f]-quinoline (III) but there is a possibility of formation of benzo[g]quinoline type compounds according to the mode of cyclization. Therefore, 3-methylbenzo[f]-quinoline (VII), m.p. 82-83°, was prepared from (III) but since its constants agreed with those given in past literature, benzo[g] quinoline type compounds were found to be not formed in this reaction. In the case of m-aminophenol, the condensation occurs only in the vacant position adjacent to the hydroxyl and 2-methyl-3-(2-chloromethyl)-4-chloro-7-quinolinol (X) alone was produced. The fact that the compounds of 5-quinolinol type was not formed in this reaction was proved by derivation of (X) to 2-methyl-7-quinolinol (XIV).
When 2-[1-(3-nitrophenylimino)ethyl]-γ-butyrolactone is heated with phosphoryl chloride, a 7-nitroquinoline-type compound, 4-methyl-7-nitro-2, 3-dihydrofuro[2, 3-c]-quinoline (II), is formed, with a small amount of 3-(2-chloroethyl)-4-chloro-7-nitroquinaldine (III) as a by-product. When a mixture of 2-acetyl-γ-butyrolactone and phosphoryl chloride is heated, 7-nitro compound (II) and a 5-nitro compound, 3-(2-chloroethyl)-4-chloro-5-nitroquinadine (IV), are formed in 5:4 ration. Heating of (II) further with phosphoryl chloride results in its conversion to (III), while heating of (III) with acetic acid regenerates (II). Therefore, it is found that these compounds are cyclization products of the same type. (IV) and 4-methyl-9-nitro-2, 3-dihydrofuro[3, 2-c]quinoline (V) also undergo the same reaction. (III) was derived to 2-methyl-3-(2-chloroethyl)-4-chloro-7-quinolinol (VII) and the positions of nitro group in (II) to (V) were confirmed.
A new method for the determination of alkoxyl group is described. In this method, a sample containing an alkoxyl group is boiled with hydriodic acid, the alkyl iodide that distills out is passed through an absorption funnel, filled with porous silver granules and heated to 400-500°, to decompose alkyl iodide and absorb iodine in silver, and the weight increase of the absorption funnel is measured. The absorption funnel is made of translucent quartz and filled with 2g. of silver granules, which can be used for continuous analyses to 100-150 times. Distillation of alkyl iodide is made for 40 minutes in the case of methoxyl and 60 minutes in the case of ethoxyl group under introduction of air through the apparatus at the rate of 10cc./min.
Pschorr reaction of sodium 3, 4-methylenedioxyphenylacetate or sodium 3, 4-methylenedioxy-6-bromophenylacetate with o-nitrobenzaldehyde afforded 2, 3-or 3, 4-methylenedioxyphenanthrene. The latter had a slightly different melting point from that of a substance assumed to be 3, 4-methylenedioxyphenanthrene, obtained by the Hofmann degradation of anonaine and roemerine, but the picrates of the two substances melted at the same temperature.
Pschorr reaction of 4-methoxy-2-nitrobenzaldehyde and 3, 4-methylenedioxyphenylacetic acid afforded 3-methoxy-5, 6-methylenedioxy- (VIII) and -6, 7-methylenedioxy-9-phenanthrenecarboxylic acid (VII). These structures were determined by carrying out the same reaction with 3, 4-methylenedioxy-6-bromophenylacetic acid. Decarboxylation of (VIII) and (VII) respectively afforded 3-methoxy-5, 6-methylenedioxyphenanthrene (I) and 3-methoxy-6, 7-methylenedioxyphenanthrene (II).
It has been found that the potency assay of various analgesics required comparison of values obtained by various methods of different nature such as the hot-plate, electrical stimulation, and heat radiation methods. Multiple experiment using these three methods was employed in examining the effect of autonomic agents, autonomic blocking agents, central stimulants, histamines, antihistamines, and antipyretics on the analgesic action of morphine and Ohton (1, 1-dithienyl-3-dimethylamino-1-butene), after subcutaneous injection of a comparatively small and a large dose into mice. It was thereby found that analgesic effect differed entirely according to the dose of either analgesics and the dose of each of the agents tested. Therefore, there is no definite relationship between the appearance of an analgesic effect and adrenergic or anticholinergic agents.
Examinations were made on the role of hypophysis and adrenals in the appearance of analgesic activity by using normal, adrenalectomized, and hypophysectomized animals. 1) Appearance of analgesic effect from morphine requires DOCA and hydrocortisone from adrenal cortex rather than epinephrine from adrenal medullary. Hypophysis, especially the frontal, is not so necessary as adrenal. 2) Oxygen consumption by cerebrum homogenate is inhibited on addition of hydrocortisone but this inhibition becomes less on further increase in the amount of hydrocortisone added. Addition of DOCA on the contrary increased the inhibition of oxygen consumption with increasing amounts. 3) Oxygen consumption by liver homogenate behaved in contrast to the case of cerebrum, both hormones increasing the oxygen consumption. In this case, oxygen consumption tended to become greater with increasing amount of hydrocortisone. 4) Oxygen consumption by cerebrum or liver homogenate was inhibited by both morphine and Ohton but concurrent use of adrenocortical hormone fortified this inhibition as an additive effect of each substance alone.
Following the syntheses of compounds possessing A-ring of tetracyclines or its partial structure, the compounds synthesized were tested for antibacterial and antifungal activies but none gave any marked effect except 2-methylcarbamoylcyclohexane-1, 3-dione which inhibited the growth of Staphylococcus aureus in a concentration of 125γ/cc.
Following structural determination of insulanoline (I), isolated from the rhizome of Cyclea insularis (MAKINO) DIELS together with norcycleanine, examinations were made on the latter base. Cleavage reaction of O-ethylnorcycleanine (V) with sodium in liquid ammonia afforded, as the bisected phenolic bases, l-armepavine (VI) and a base identified as l-1-(4-hydroxybenzyl)-2-methyl-6-methoxy-7-ethoxy-1, 2, 3, 4-tetrahydroisoquinoline (VII). This has confirmed that the structure of norcycleanine would be represented by the formula (III).
Colorless needle crystals of m.p. 162-162.5° were obtained, together with benzoic acid, from dried leaves of Abies Mariesii MAST. (Pinaceae). The substance agreed in composition to C6H6O3 and properties of its derivatives all agreed well with those of maltol (2-methyl-3-hydroxy-γ-pyrone) described in past literature. Maltol had heretofore been obtained from aciculate leaves of Abies pectinata DC. and trunk bark of Larix europaeae DC., and it was newly obtained from A. Veitchii LINDLEY and Tsuga diversifolia MAST. by the present authors. It was not detected, however, in Abies firma SIEB. ET ZUCC. and from Tsuga Sieboldii CARRIERE.
A substance of C15H18O3, melting at 153.5-155°, was isolated in 0.03-0.04% yield from Artemisia kurramensis QAZ. and this substance was found to be entirely identical with lumisantonin, one of the products formed by ultraviolet irradiation of l-α-santonin.