It has been found that in the colorimetric determination of kainic acid with ninhydrin, preliminary addition of benzene to the reaction system effects stabilization of the reaction and increased sensitivity of the coloration. The presence of over 2 molar volumes of amino acid or ammonium salts interferes with the determination but the presence of sugar and inorganic salts in the amount usually present in Digenea was found to be negligible.
Hardness meter for tablets against static pressure using a lever was manufactured on trial and its effect on transition rate of the load, overlapping of the switch, and variation of the load were examined in order to certify the reliability of the hardness meter. On using this hardness meter, the following points were clarified: 1) When the thickness of the tablet was varied, there was a large interaction with the degree of compression, even when same granules are used. 2) As for the die of tabletting, one with a smaller radius of curvature makes soft tablets. 3) As for the relationship between tabletting and crumbling time, (a) use of soft granules does not show any effect of die type between time of crumbling and hardness; but (b) use of hard granules show the effect of die type, and the die of 9mm. diameter and γ′=6.75mm. was found to give tablets of equal hardness which crumble rapidly.
Organic mercurial diuretic (pyridine-2, 3-dicarboxylic acid allylamide mercury hydroxide Na salt + theophyllin) was administered by the intravenous injection, and the amount of mercury in the compound of the original structure excreted into urine and the amount of total mercury obtained by the decomposition of urine were periodically followed by polarography. The total mercury was measured by the wave height of a solution obtained after decomposition of 20cc. of the sample urine with about 1/4 volume of a mixed acid (H2SO4:HNO3=1:3), a definite amount of alkali added, and diluted to 20cc. with water. Organic mercury was determined by the measurement of the wave height of the polarogram of a solution prepared by diluting the sample urine with an equal volume of the Sörensen buffer of pH 8.4. The concentration of mercury excreted was the maximum 1 hour after the injection, decreased rapidly thereafter, and the amount excreted levelled off after 3-5 hours, the amount being almost independent of the amount of urine. The amount of mercury excreted in a healthy human was about 70% of the dose administered 24 hours after injection but was about 70% after 48 hours in sick persons. The amount of organic mercury excreted was approximately equivalent to that of total mercury. It is assumed, therefore, that most of mercury is excreted in the original state, not having undergone any change.
The mercuration of 6-methylquinoline 1-oxide, 4-bromoquinoline 1-oxide, and 8-bromoqulnoline 1-oxide with mercuric acetate, followed by treatment with sodium chloride, respectively, yielded 8-chloromercuri-6-methylquinoline 1-oxide, 8-chloromercuri-4-bromoquinoline 1-oxide, and 4-chloromercuri-8-bromoquinoline 1-oxide, which were confirmed by deriving them to bromoquinolines. These facts show that the 8-position in quinoline 1-oxide series is much more susceptible to mercuration than the 4-position. The mercuration of 2-bromoazoxybenzene and 4-bromoazoxybenzene with mercuric acetate respectively, yielded 4- and 2-mercurated derivatives. These were treated with bromine to give 2, 4-dibromoazoxybenzene and were identified as such. Tentative reaction mechanism was proposed.
The mercuration of benzyl alcohol with mercuric acetate, followed by treatment with sodium chloride, yielded o-chloromercuribenzyl alcohol (61%), p-chloromercuribenzyl alcohol (15%), and polychloromercuri compound (24%) The position of the mercury atom in the mercurials was verified by their successive treatment with potassium permanganate and iodine, and deriving them to iodobenzoic acids. One of the polymercurated products turned out to have been 2, 5-dichloromercuribenzyl alcohol. On treatment with iodine, o- and p-chloromercuribenzyl alcohol gave corresponding iodobenzyl alcohols in high yields. This affords a new and convenient method for the preparation of o-halogenated benzyl alcohols.
Erucyl alcohol was found as the higher alcohol in the non-saponifiable matter of the globefish ovaries and its structure was confirmed by the hydrogenation reaction, oxidative decomposition, and synthesis.
Application of alkanethiol, alkyl alkanethiolsulfinate, or sodium alkylthiosulfate to thiamine disulfide (I) results in the formation of thiamine alkyl disulfide. The amount of thiamine alkyl disulfide formed from (I) and alkanethiol is barely detected by paper partition chromatography but the amount formed increases if (I) is preliminarily oxidized with hydrogen peroxide. In such a case, the formation of a sulfoxide, sulfodioxide (IX), and sulfenic acid derivative (X) of (I) can be assumed as intermediates
It has been clarified that the application of acetyl or propionyl chloride to p, p′-ditolyl ether, in the presence of aluminum chloride, results in intermediate formation of the corresponding 2, 7-dimethyl-9-alkylxanthenol and that the reaction proceeds further with occurrence of various side-reactions. In this case, application of phenylacetyl chloride was found to give 2, 7-dimethyl-9-benzalxanthene, m.p. 103-105°, in a good yield.
The reaction whereby the application of acetyl chloride to 4-methoxy-4′-methyl-or 2, 3-dimethoxy-4′-methyl-diphenyl ether results in the occurrence of xanthenol cyclization to form the corresponding xanthone compounds was examined. It was found that the same xanthenol cyclization occurred with 2-acetyl-, 2-acetyl-4, 4′-dimethyl-, 2-acetyl-4, 5-dimethoxy-, 2-acetyl-5, 6-dimethoxy-4′-methyl-, and 2-benzoyl-diphenyl ethers, with carbon disulfide as the solvent and in the presence of aluminum chloride, and when conc. sulfuric acid was added. Some presumptions on such abnormal reaction mechanism were forwarded.
It has been shown that the application of methyl oxalate chloride, in the presence of aluminum chloride, to p, p′-ditolyl, 3, 4-dimethoxydiphenyl, and 4-methoxy-4′-methyldiphenyl ethers gave the corresponding 9-hydroxyxanthene-9-carboxylates. The free acids formed by the saponification of these esters easily underwent oxidation by hydrogen peroxide to form the corresponding xanthone derivatives. Boiling of methyl 2, 7-dimethyl-9-hydroxyxanthene-9-carboxylate with ethanol, methanol, or butanol resulted in facile etherification of the hydroxyl in the 9-position by these alcohols.
D-Strain of Penicillium islandicum Sopp was cultured in Czapek-Dox (5% glucose) medium for 14 days at 32-33° and the mycelium and the filtrate were separated. Treatment of the filtrate by adsorption with carbon yielded malonic acid, m.p. 135-136°, with the toxicity of LD50 1.4mg./10g. mice. The mycelium was treated with acetone and the acetone extract (M. L. D. 20mg./10g. mice) was extracted consecutively with petroleum ether, ether, chloroform, methanol, acetone, and water. Of these six fractions, the toxicity of the ether and methanol portion respectively was 20mg. and 10mg. per 10g. mice. Ergosterol, m.p. 162-164°, and islandicin, m.p. 216°, were isolated and identified from the petroleum ether fraction. Methanol fraction revealed the presence of D-mannitol and the presence of a hygroscopic toxic substance was indicated. Pigments in each fraction were preliminarily examined by paper chromatography.
The presence of vitamin B group-like factors in domestic lichens, Usnea acciculiphera (I), Parmelia tinctorum (II), and Cladonia subtenuis (III), was examined by microbiological assay and following results were obtained: Biotin-(I) 140mγ/g., (II) 113mγ/g., (III) 55mγ/g. Pantothenic acid-(I)>1γ/g., (II) 0.8γ/g., (III) 0.3γ/g. Nicotinic acid-(II) 44mγ/g., (III) 15γ/g. Vitamin B12-(I) 12mγ/g., (II) 8mγ/g., (III) 4mγ/g. Antibacterial action against Escherichia coli and several other bacteria was examined with 50% methanolic extract of (I) and (III) and methanolic extract of (II) but none showed any marked antibacterial action except the extract of (III) which was effective against Bacillus subtilis. The aqueous solution obtained by the high-pressure extraction of (I) with water was found to contain a factor which inhibited the growth of Lactobacillus arabinosus.
The content of chlorophyll in some commercial toothpastes containing chlorophyll was determined using a quantitative bridge. A quantitative bridge of 2mm.-width and 60mm. length was made at a position 60mm. from the starting line and the paper was developed at 25° with a mixture of butanol: ethanol: 1% ammonium chloride solution (2:1:1). Calibration curves shown in Figs. 1-3 were obtained. The accuracy by this method was within 4.3-4.6% and better results compared to the existing method were obtained.
Of the three isomers (m.p. 155°, 164°, and 202°) of α-(3-oxo-9-methyl-3, 5, 6, 7, 8, 9-hexahydro-6-naphthyl) propionic acid, those of m.p. 155° and 164° were assumed to be 3-oxo-4-noreusantona-1, 4-dienic acid and its 11-epi compound, in which the angular methyl in both is in axial conformation and the propionic acid chain is equatorial, with only the conformation at C11 different. In order to prove this point, 3-oxo-4-nor-isoeusanton-4-enic acid, in which the acid side-chain takes the axial conformation, and 3-oxo-4-noreusanton-4-enic acid, in which the acid chain takes the equatorial conformation, were synthesized by different routes and by the comparison of the reduction products from these four compounds, the assumption for the 1, 4-dienic acids was found to have been correct. On the other hand, the isomer of m.p. 202° was assumed to be 3-oxo-4-nor-isoeusantona-1, 4-dienic acid possessing both the angular methyl and the acid sidechain in the axial conformation.
Attempts were made to change the bromine atom in 6-bromo-3-oxo-4-noreusantona-1, 4-dienic acid, 6-bromo-3-oxo-11-epi-4-noreusantona-1, 4-dienic acid, and the ester of the 11-epi compound, directly with hydroxyl or acetoxyl and to allow formation of a lactone with carboxylic acid side-chain at C11, so as to derive them to 4-norsantonin but the bromine at C6 easily underwent liberation to form 1, 4, 6-trienone derivatives possessing a double bond at C6-C7. Lactonization was then attempted with ethyl 6-bromo-11-ethoxycarbonyl-3-oxo-4-noreusantona-1, 4-dienate, possessing another carboxyl group at C11, from which 11-carboxy-4-norsantonin (lactone: cis) was obtained. Its decarboxylation was carried out but the formation of 4-norsantonin could not be proved.
Treatment of the dibromo compound, obtained by the bromination of 3-oxo-11-epi-4-noreusantona-1, 4-dienic acid, with a base yields bromo-3-oxo-11-epi-4-noreusantona-1, 4, 6-trienic acid and one of rac-bromo-4-norsantonins (lactone: cis). The position of the bromine in these compounds was assumed to be at C2. Attempted debromination of this rac-bromo-4-norsantonin (lactone: cis) and derivation to rac-4-norsantonin (lactone: cis) ended fruitless.
2-Bromo-4-nordihydrosantonin, obtained by the bromination of 3-oxo-4-norisoeusanton-4-enic acid and 3-oxo-11-epi-4-noreusanton-4-enic acid, was submitted to dehydrobromination but 4-norsantonin was not obtained. Dehydrobromination of 2-bromo-11-carboxy-4-nordihydrosantonin (lactone: cis), obtained by the bromination of 11-carboxy-3-oxo-4-noreusanton-4-enic acid, also failed to yield 4-norsantonin. However, dehydrobromination of a crude brominated compound yielded 2-bromo-4-norsantonin which was assumed to be 2-bromo-6β-hodroxy-3-oxo-11-epi-4-norsantona-1, 4-dienic acid lactone.
3-Oxo-4-noreusantona-1, 4-dienic acid and its 11-epi compound were submitted to lactonization by heating with selenium dioxide and rac-4-nor-α-santonin (lactone: trans) and rac-4-nor-β-santonin (lactone: trans) were obtained. Both rac-4-norsantonins were submitted to rearrangement through treatment with acetic anhydride and sulfuric acid from which rac-4-nor-α-desmotroposantonin acetate and rac-4-nor-β-desmotroposantonin acetate were obtained, which were saponified with sodium carbonate respectively to rac-4-nor-α-desmotroposantonin and rac-4-nor-β-desmotroposantonin, to confirm their respective structures. It was found that rac-4-nordesmotroposantonin acetate tended to undergo isomerization at C11 during saponification with alkali.
Mutual solubilities in the nicotine-water-sodium hydroxide system at 0°, 30°, 60°, and 90° were measured and equilibrium diagrams were drawn. Conjugation curve, drawn with the concentration of sodium hydroxide in the lower layer of the conjugate solution as the abscissa and the concentration of nicotine in the upper layer as the ordinate, was found to become linear within a limited concentration range when the concentration unit is shown by molar fraction, although the curve deviates from the straight line in the extremely low or high concentration. These curves at various temperatures run almost parallel. The composition of the conjugate solution comes to be over 90% nicotine in the upper layer when the amount of sodium hydroxide in the lower layer is over 20%, and the lower layer is practically devoid of nicotine, with none of sodium hydroxide in the upper layer. Except in the case of 0°, the upper layer present with 35-40% sodium hydroxide solution is almost 100% nicotine. The concentration of nicotine in equilibrium with a definite concentration of sodium hydroxide solution increases with the increase of temperature. The present experimental results have offered advantageous method for the isolation and dehydration of nicotine.
In the extensive investigation of the alkaloids contained in domestic aconites throughout Japan, herbarium of each plant was numbered, pending complete classification, and the results of alkaloidal analyses are reported herein. The rhizome, stem, and leaves of collected near the peak of Mt. Mitake (Tokyo prefecture) (Ochiai No. 8; possibly the aconite Aconitum mitakense Nakai according to Prof. Nakai) yielded 0.15% (against the fresh plant) of total alkaloids by extraction and this was separated into water-soluble portion and ammonia-precipitate. From the latter, crystalline alkaloids, aconitine (11.7%), mesaconitine (6.2%), jesaconitine (0.9% as the perchlorate), and ignavine (3.2%) were obtained. During chromatographic separation, jesaconitine comes out in the aconitine mesaconitine fraction. In order to follow the manner of this separation, separatory determination through ultraviolet spectral measurements of benzoyl- and anisoyl-alkamines was devised. It was thereby found that the composition ratio of the two could be determined by measuring the optical density of unknown samples at 231mμ and 259mμ, and comparing their ratio with the calibration curve drawn with the optical density ratio of benzoylalkamine at 231mμ and of anisoylalkamine at 259mμ as the ordinate and the percentage composition of the two compounds as the abscissa.
Alkaloidal components were extracted from the aconite collected at Toroko (Akita Prefecture) (Ochiai No. 9) and at Gomando (Fukushima Prefecture) (No. 10) yielded, as the crystalline alkaloids, aconitine and Toroko-base I (tentative designation) from the ammonia precipitate, Toroko-bases II, III, and IV (all tentative designations) from the water-soluble portion and jesaconitine (as perchlorate) from the ammonia precipitate. Toroko-base I comes as needle crystals melting at 198-200° (sinters once at 130-140°), [α]D10: +77.71° (MeOH), has a benzoyl group, but its composition has not been determined as yet. Toroko-base II comes as needle crystals of m.p. 85-88°, [α]D12: +43.45° (MeOH), agrees with C24H39O6N, and possesses three methoxyls and one N-methyl (or N-ethyl) group. Toroko-base III, m.p. 325-326° (decomp.), and Toroko-base IV. m.p. 207-209°, have not been characterized as yet. Ammonia precipitate of No. 10 base yielded jesaconitine, mesaconitine, and a base clearly different from jesaconitine and possessing an anisoyl group and this was tentatively designated as the Gomando-base II. It failed to form a crystalline perchlorate. Another base, possessing a benzoyl group, was obtained as needle crystasls of m.p. 199° (sinters once at 140°), [α]D20: +76.60. Its mixed fusion with the Toroko-base I showed no depression of the melting point but the analytical values did not agree that it was tentatively designated as the Gomando-base I. A base was obtained as needle crystals of m.p. 320° (decomp.) from the water-soluble portion and was tentatively designated as the Gomando-base III pending clarification of its composition.
Relationship between the minimum reflactance (R%) and the concentration of a dye (mg. per 100cc.) was examined with a filter paper staind by various dye solutions for foodstuffs. When the value of 2-logR is plotted against the value of √c (c is the concentration of the dye solution in mg./100cc.), approximately linear relationship was found to hold within a certain range of dye concentrations. Similar relationship was also found to hold between the minimum reflactance of the filter paper spotted with such dye solutions and the amount of the dye (γ) in a spot.
Two kinds of steroidal sapogenins were isolated from the total plant or the rhizome of Reineckia carnea Kunth, a Liliaceous plant originating in Japan and China. One came as needle crystals of m.p. 208-210° and was characterized as diosgenin by admixture and elemental analyses. The other melted at 298° and its analytical values agreed with C27H44O6, and the analytical values of its acetate, m.p. 226°, agreed with triacetate, C33H50O9. The infrared absorption spectrum of this acetate showed the characteristic absorption band of 22-isosteroidal sapogenins and the absence of carbonyl and presence of one hydroxyl not undergoing acetylation were assumed in this molecule. It seemed to be a new steroidal sapogenin and the name of kitigenin was given for it.
The amount of calcium in a solution of calcium salt with the concurrent presence of magnesium salt was determined by adding a small amount of ammonia to such a solution, adding ammonium molybdate solution in the presence of ammonium salt, and warming on a boiling water bath. The calcium molybdate precipitate thereby formed was collected by filtration, washed with boiling water, dried, and ignited. In this case, the mother liquor shows approx. pH 6.0. The amount of magnesium in the filtrate was determined by the method elaborated by the present author. In the formation of calcium molybdate, a part of barium precipitates at pH 5.8 but strontium was found to be without effect. Magnesium remains dissolved at around pH 5.8-9.2 and its separate determination by later procedures was found to be possible.
Pharmacological action of 1, 1-diphenyl-3-piperidinobutanol hydrochloride (No. 3) was examined and following results were obtained: 1) In the tests on antispasmodic activity by the excised guinea pig intestines, No. 3 showed 30-50% activity of atropine sulfate and 50% that of papaverine hydrochloride, and in vivo intestinal tests, it showed approximately 8% the activity of atropine sulfate. 2) The local anesthetic activity of No. 3 was 70% of procaine hydrochloride as inducing anesthetic, and 270% of procaine as surface anesthetic. 3) The side-action of No. 3, as compared to that of atropine sulfate, was less than 1/50 in antisilagogue action, less than 1/60 in vagal cardiac stimulating action, and less than 1/50 in mydriatic action. Its LD50 was 59.7mg./kg. by intravenous injection.
In order to synthesize asebogenin, the aglycone of the glycoside, asebotin (2-hydroxy-4-methoxy-6-glycosidoxy-ω-(4-hydroxyphenyl) propiophenone), by the methylation of C4-hydroxyl group in phlorhizin, condensation of phloretic nitrile and ω, ω, ω-trichloro-2, 4-dihydroxy-6-methoxyacetophenone in ether solution, with zinc chloride, was carried out. The oily product thereby formed was warmed with sodium hydrogen carbonate solution at 50°, liberating chloroform, and the acid formed was extracted with ether in hydrochloric acidity. The ether residue was warmed with water and a minute amount of methanol to effect decarboxylation, from which microneedles, m.p. 166-168°, were obtained and it was identified with the natural asebotin.
In order to examine the reaction of the hydroxamic acids of higher fatty acids and ferric ion and other metals, color reaction between the hydroxamic acid of oleic acid and Fe... was examined. It has been found that, when abs. ethanol is used as the solvent, the complex with the the molar ratio of Fe... and hydroxamic acid of 1:1 (coloration: reddish purple with absorption maximum at 525mμ), of 1:6 (reddish brown, absorption maximum at 490mμ), and of various intermediate ratios (reddish brown with all absorption maximum at 490mμ) are formed while the use of petroleum ether as the solvent does not yield the complex of 1:1 molar ratio. It was also seen that this color reaction of the hydroxamic acid of oleic acid with Fe... can be utilized for the colorimetric determination of the hydroxamic acid and its conformity to the Beer's Law was also proved.
Absorption spectra were measured of the ferric complex of the hydroxamic acids of oleic, petrosellic, petrosellidic, and erucic acids, at the molar ratio of Fe... to hydroxamic acid at 1:1 and 1:6. From the agreement of absorption spectra in the visible range, which is responsible for the coloration, it was assumed that the manner of bonding of the hydroxamic acid and Fe... was the same in the 1:1 and 1:6 molar ratios. It was found that there also is an absorption maximum in the near-infrared region, and an absorption in the ultraviolet region which is different with different hydroxamic acid used. Calculation of the energy difference between the fundamental state and the excited state indicated that the complex with molar ratio of 1:1 is more unstable than that of 1:6 molar ratio and this fact was supported by the experiments using salicylic acid.
It was found that the addition of acids, compounds possessing coördinatively unsaturated oxygen atom, and compounds possessing highly negative groups to the abs. ethanolic solution of the mixture of Fe... and the hydroxamic acid of oleic acid, in the molar ratio of 1:1 and 1:6, effected disappearance or fading of the color of such a solution and the experiments were carried out with acetic acid, lactic acid, ether, acetone, water, and pyridine as representative of the foregoing groups of compounds. It was thereby found that the complex of 1:1 molar ratio was more easily affected by various substances than that of the 1:6 molar ratio and that the former underwent change after converting once to the complex with 1:6 molar ratio. This endorses the previously reported fact that the complex of 1:1 molar ratio is more labile than that of 1:6 ratio. The change of the former into the latter before undergoing further change indicates that the bond in 1:1 complex is severed but it is still uncertain whether the complex of 1:6 ratio is severed of its bond by the above-mentioned substances or such substances attach additively to the complex of 1:6 molar ratio.
Cocaine hydrochloride, tropacocaine hydrochloride, homatropine hydrobromide, and scopolamine hydrobromide can be potentiometrically titrated in anhydrous acetic acid with perchloric acid by glass-calomel electrodes, if mercuric chloride is added in excess of the molar equivalents of the sample. Atropine can also be accurately titrated directly but the titration of its sulfate was not so accurate. The presence of glucose or ethanol was not found to interfere in this titration. These tropane alkaloids can accurately be determined with one mole as one equivalent by titration with crystal violet as the indicator. These titration curves suggested that the basicity of l-cocaine in glacial acetic acid was the strongest, followed by l-scopolamine, and the weakest were tropacocaine, homatropine, and atropine, which were approximately of the same basicity.
1) Percentage of alkaloidal content in the leaves was compared by the concurrent cultivation of the diploid and tetraploid Datura and it was found that alkaloidal percentage in the tetraploid leaves was double that of the diploid. The amount of dried leaves per 300-tsubo area was also 1.5 times greater. 2) Alkaloidal content was the maximum (0.810%) on June 20th, showed a slight decrease thereafter, was 0.71% for one month from June 30th, maintained the level of 0.59% during the flowering and rapidly decreased to 0.38% during October. 3) The total alkaloidal content in the leaves gradually increased with the growth, attained the highest of 0.816g, on July 30th, then gradually decreased, suddenly from September 20th, and was 0.420g. around October 20th.
The oily product (I) of b.p25 67° obtained by the soda-lime dry distillation of kainic acid was derived to a few crystalline derivatives from which the structure of (I) was assumed as β-isopropylpyrrole, C7H11N, and not α-methyl-β′-isopropylpyrrole as reported before. This new structure was confirmed by identity with the synthetic specimen and the fact is hereby corrected.
2-(ω-Dimethylaminoalkyl) pyridine, 1-aza[5, 4, 0]bicyclohendecane, and related compounds, with 1-5 carbon atoms in the side-chain alkyls, were synthesized. Accorcing to Prof. Misawa of the University of Tokyo, the cholinergic action of the methiodide of the foregoing pyridine compounds was the strongest when there in only one carbon in the side-chain alkyl, decreased rapidly at 2 carbons, and decreased further as the number of carbon increased from 3 to 5. However, there was no evidence that these compounds underwent change from cholinergic to ephedrine-like action, as in the case of phenylalkyltrimethylammonium salts.
Effect of the vitamin addition during coagulation of milk by lab ferment was examined and it was found that the addition of vitamin B1 and C accelerated coagulation while vitamin B2, B12, and K inhibited coagulation. The acceleration of milk coagulation by vitamin B1 and C was found to be mainly due to their acidity and only slightly by the fundamental nature of these vitamins.
Mold-preventive action of 15 kinds of compounds against soy sauce was examinined and it was found unexpectedly that none of them possessed marked action up to about 0.01% concentration. The compounds tested were as follows: Quinoxaline, pyrazine-carboxylic acid, methyl pyrazine-carboxylate, pyrazine-carboxyl amide, pyrazine-2, 3-dicarboxylic acid, dimethyl pyrazine-2, 3-dicarboxylate, pyrazine-2, 3-dicarboxylic acid diamide, pyrazine-2, 3-dicarboxylic acid dihydrazide, nicotinic acid, methyl nicotinate, nicotinic acid hydrazide, 2-chloro-6-methyl-4-isoamylresorcinol, 2-chloro-6-methyl-4-hexylresorcinol, 3, 3′-dicyclohexyl-4, 6, 4′, 6′-tetrahydroxydiphenyl, and agaricic acid trihydrazide.
Pieris japonica collected in Nara and Hiei region contains asebotin but that collected in the Rokko, Takarazuka, and Tada regions contains phlorhizin instead of asebotin, although the two kinds of plants cannot be discriminated morphologically. The inconsistency that the presence of asebotin in Kalmia latifolia (Ericaceae, the same family as that of the above plant) by Bourquelot and Fichtenholz was denied by Bridel and Kramer, who claimed the presence of phlorhizin, may have been due to the fact that the difference in habitat resulted in the different componental substances, as evidenced by the foregoing example.
Ethyl 6-oxodecanoate was prepared from ethyl adipate chloride and butyl iodide, with zinc-copper catalyst, the carbonyl group reduced, and brominated with hydrogen bromide to methyl 6-bromodecanoate. Its dehydrobromination with quinoline yielded a mixture of methyl 6- and 5-decaenoate.
Dehydrobromination of 5, 6- and 6, 7-dibromodecanoic acids, obtained by the bromination of methyl 5- and 6-decaënoate, with quinoline yielded 5- and 6-decayne-1 acid, and not the unsaturated fatty acid with a conjugated double bond.