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TAKASHI MATSUI, MITSUO NAGANO, TAKESHI KINOSHITA
1974 Volume 94 Issue 5 Pages
533-539
Published: May 25, 1974
Released on J-STAGE: May 30, 2008
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A role of proton and heavy metallic ions in the desulfurization ring-closure reaction of 4-(o-aminophenyl)-3-thioallophanic acid ester (Ib) is discussed from the concept of charge and frontier controlled reactions based on a quantum chemical perturbation theory. It is assumed that the protonation to Ib may occur at the position of O-12, S-13, and N-14 atoms but heavy metallic ions, which are known as soft acids, make the selective coordination at the position of S-13, which has the largest highest-occupied density. The energy change in the π-conjugated intramolecular ring-closure reaction is estimated from the perturbation term by the HMO approximation on the assumption that the increase of Coulomb integrals h
O12, h
S13, and h
x14 may be caused by the protonation. The increase of h
S13 and/or the decrease of h
x14 makes the partial bond orders P
HO8, 13 negative and P
HO8, 14 positive resulting in the decrease of P
8, 13 and the increase of P
8, 14 Namely, the protonation to S-13 (the increasing electronegativity of S-13) suggests the tendency of the formation of a new bond between C-8 and N-14, and the weakening of the bond between C-8 and S-13. However, the protonation to O-12 or N-14 (the increasing electronegativity of O-12 or N-14) suggests the opposite tendency. It is understandable that the presence of heavy metallic ions which may cause the selective addition to S-13 accelerates the ring-closure reaction of Ib.
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KAZUO TAKAYAMA, KAZUNOBU HARANO, TANEZO TAGUCHI
1974 Volume 94 Issue 5 Pages
540-547
Published: May 25, 1974
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When 1-(P-chlorobenzoyl)-3, 3-dimethylindolin-2-ylpyridinium chloride (IIa) was pyrolyzed in pyridine, 1-(p-chlorobenzoyl)-2, 3-dimethylindole (Va) was obtained together with a pair of geometrical isomers consisting of C
27H
25ON
2Cl (M
+428). The isomers were characterized as 5-(p-chlorobenzoyl)-5a, 5b, 6, 11a-tetrahydro-5a, 6, 6, 11a-tetramethylindolo-[1, 2 : 1', 2']azetidino[3, 4-b]indole (IIIa-1, 2) on the basis of mass and nuclear magnetic resonance spectral data. An additional structual proof for IIIa-1, 2 was provided by the formation of 5-(p-chlorobenzyl)-5a, 5b, 6, 11a-tetrahydro-5a, 6, 6, 11a-tetramethylindolo-[1, 2 : 1', 2']azetidino-[3, 4-b]indole (VI), 2, 3-dimethylindole (VII), and 3, 3-dimethylindoline (VIII) by the reduction of III with lithium aluminum hydride. 3-Methyl-3-ethyl (XIIIa) and 3, 3-diphenyl (XIIIc) analogs of IIa showed the same behavior as IIa by pyrolysis.
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KAZUO TAKAYAMA, KAZUNOBU HARANO, TANEZO TAGUCHI
1974 Volume 94 Issue 5 Pages
548-552
Published: May 25, 1974
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In connection with studies on pyrolysis of 3, 3-disubstituted 1-acyl-indolin-2-ylpyridinium chloride,
1) 2, 3, 3-trisubstituted 1-acyl-indolin-2-ylpyridinium chlorides (Ia-c) were analogously pyrolyzed in boiling pyridine. Of the compounds treated, only derivatives holding a methyl substituent at position 2 (Ib, c) underwent pyrolysis giving 3, 3-disubstituted 1-(p-chlorobenzoyl)-2-methylene-indoline (IIb, c). During the isolation of IIb and IIc, 1-(p-chlorobenzoyl)-2, 3-dimethyl-3-phenylindolin-2-ol (IVb) and 3-[2-(p-chlorobenzoyl-anilino)]-3-methyl-2-butanone (IIIc) were respectively found in the reaction mixture. The tautomeric character of these compounds (IVb and IIIc) existing in the indolin-2-ol and its ring opening structures in solution was discussed. Additionally, this report involves a correction of the product in the Friedel-Crafts reaction of 1-benzoyl-2-chloro-3, 3-dimethyl-indoline with benzene reported by Leuchs.
3)
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HIROSHI SHIRAKI, EIKO TAKAGI, KAZUYUK MINEURA, HIROSHI TAKAHIRA
1974 Volume 94 Issue 5 Pages
553-558
Published: May 25, 1974
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The metabolic fate of
14C-KW-110 in rats has been studied. After oral administration of 500 mg/kg of
14C-KW-110 to rats, the radioactivity excreted was 73.3% in expiratory CO
2, 16.4% in feces, and 8.2% in urine, whereas aluminum it KW-110 was excreted in feces only. After the oral administration of KW-110 to rats, the radioactivity was distributed in all tissues in rats and especially high i0n stomach, intestinal tracts, liver, and kidney, but aluminum in KW-110 administered was distributed only in digestive tracts, and retained in stomach for about 5-7 hr after its oral administration and gradually moved into intestinal tracts. N-Acetylglutamine, glutamine, -and urea were identified as urinary radioactive metabolites after the oral administration of KW-110 and they accounted for 46.5%, 24.7%, and 27.4%, respectively, of total radioactivity excreted in 48-hr urine. The radioactive substances detected in serum were also N-acetylglutamine, glutamine, and glutamic acid.
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HIROSHI SHIRAKI, KAZUYUK MINEURA, HIROSHI TAKAHIRA
1974 Volume 94 Issue 5 Pages
559-565
Published: May 25, 1974
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Effect of oral administration of KW-110 on gastric juice components was examined in Shay rats. Following an oral administration of KW-110, the volume of gastric juice was not changed but the pH of gastric juice was increased. Further, protein contents and peptic activity in gastric juice were lowered, while aluminum content in the stomach wall was raised. The binding of aluminum to the stomach wall occurred selectively in the glandular portion. The kinds of protein decreased in gastric juice after the oral admini-stration of KW-110 was found to be nonspecific judging from the molecular distribution in the experiments with Sephadex G-75 gel filtration. Aluminum in orally administered KW-110 might be bound to protein secreted in the glandular stomach. These results were emphasized by the polyacrylamide gel electrophoresis of aluminum-protein complexes ; the electrophoretic pattern of protein in normal gastric juice was consistent with that of protein which was dissociated from aluminum-protein complexes and dissolved in artificial gastric juice (pH 1.2).
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MASATOMO HAMANA, MASAHIRO YATABE
1974 Volume 94 Issue 5 Pages
566-570
Published: May 25, 1974
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Quinoline 1-oxide (I) reacted with sodium nitrite and tosyl chloride in cold ethanol (-10- -20°) to afford, besides carbostyril (II), 2-nitro- (III) and 4-nitro-quinoline (IV), although in a poor yield. When carried out in anhydrous and cold dimethylformamide (DMF), the reaction followed another path and 3-nitroquinoline 1-oxide (V) was formed, accompanied by the recovery of unchanged I, small amounts of by-products being detected in some cases. After various examinations, it was found that V is obtained in 60-80% yield by the repeated treatment of I with an excess reagent under similar conditions. The formation of V seems to involve nitrosation of a dihydroquinoline intermediate followed by oxidation to a nitro compound.
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SHIGEO SENDA, KOSAKU HIROTA, OSAMU OTANI
1974 Volume 94 Issue 5 Pages
571-576
Published: May 25, 1974
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Synthesis of 1 (or 3)-phenyl-4-oxodihydropyrimidiue (11 or 12) from the corresponding 2-thiouracil derivative (4 or 5) was investigated. These compounds (11, 12) and 3, 6-dimethyl-2-phenyl-4-oxo-3, 4-dihydropyrimidine (17) were brominated to give the 5-bromo compounds (14, 15, 19), which were allowed to react with dimethylamine. The desired 5-dimethylamino compounds (2, 3) were not obtained from 15 and 19, but 5-dimethyl-amino-6-methyl-3-phenyl-4-oxo-3, 4-dihydropyrimidine (1) was obtained from 14. Analgetic and antiinflammatory activities and acute toxicity of 1 were tested to be compared with those of 1, 3-disubstituted 5-dimethylamino-6-methyluracil (A) and aminopyrine.
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HIROYUKI INOUYE, YOSHIO TAKEDA, SETSUO SAITO, HIROSHI NISHIMURA, RYOKO ...
1974 Volume 94 Issue 5 Pages
577-586
Published: May 25, 1974
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From the fruits of Gardenia jasminoides forma grandiflora, which has been employed as a Chinese crude drug, Shanzhi-i, three new iridoid glucosides, gardenoside (1), shanzhiside (3), and methyl deacetylasperulosidate (4), were isolated along with known geniposide (2) and genipin gentiobioside (5), and the structures of the new glucosides were established. Gardenoside (1) also occurs in the leaves of this plant together with geniposide (2).
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SIGERU AONUMA, TSUTOMU MIMURA, TOSHIKAZU FUKUDA, TOSHIHIDE NAKANISHI, ...
1974 Volume 94 Issue 5 Pages
587-592
Published: May 25, 1974
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The antagonistic relationship on cytolysis of bacterial protoplast and rabbit red blood cells between serum calcium-decreasing active lipoprotein α-I, which was obtained from culture filtrate of Bacillus subtilis K., and surfactin was investigated. a-I showed an inhibitory effect against the lytic activity of surfactin. Even if α-I and rabbit red blood cells were preincubated, α-I did not bind with red blood cells and remained in the supernatant. Consequently, the mechanism of antagonism between α-I and surfactin was found to be the association of α-I with Surfactin. This was also ascertained by gel filtration. On the other hand, α-I and Surfactin had no antimicrobial activity against Bacillus subtilis. Examination of the production patterns of these substances showed, that the surface activity increased rapidly in the culture medium during the logarithmic growth phase, and the antagonist α-I Was released during the stationary phase and the autolysis period, accompanied with spore formation. These results suggest that α-I and Surfactin were required as regulating factors on the growth and autolysis of Bacillus subtilis.
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TADAO FUJIE, MACHIKO OGAWA
1974 Volume 94 Issue 5 Pages
593-601
Published: May 25, 1974
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Determination of 13 kinds of sulfanilamides was attempted by thermometric and differential thermometric titrations, and heat of reaction was also calculated. Quantitative determination was made by the diazotization method using sodium nitrite and by the neutralization method using sodium hydroxide. Diazotization method by thermometric titration made it possible to determine at ordinary temperature, without the use of an indicator, and the error was within 3% to less than 0.5%. In the case of neutralization method, determination with an error of within 3% was possible by the use of 50% (v/v) acetone-water as a solvent and by slow titration speed.
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YOSHIHARU KANEO, SADAO IGUCHI, HIDEYUKI NAGATOMI
1974 Volume 94 Issue 5 Pages
602-606
Published: May 25, 1974
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A new method which can predict the in vivo binding ratio from the in vitro data is proposed. The binding of sulfisomidine with bovine serum albumin was examined using the ultrafiltration method, and the binding constant (K) and the maximum binding number (n) for sulfisomidine were found to be independent of the protein concentration. The values of n and K in the diluted sera obtained from 20 patients with chronic rheumarthritis were measured in vitro using the equilibrium dialysis method. From these data, the in vivo binding ratio at any plasma concentration of sulfisomidine was calculated theoreti-cally without using large quantities of samples. It was noticed that the higher the plasma concentration of the drug became, the more remarkable the individual variations were. This new method seems to be very useful for the comparative study of the human drug-protein binding.
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SEHCHI UENO, YOSHINORI TOMINAGA, REIKO NATSUKI, YOSHIRO MATSUDA, GORO ...
1974 Volume 94 Issue 5 Pages
607-612
Published: May 25, 1974
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Application of carbon disulfide and dimethyl sulfate to 1, 4-dioxo-1, 2, 3, 4-tetrahydro-isoquinoline (I) in ammonia water gave methyl 1, 4-dioxo-1, 2, 3, 4-tetrahydroisoquinoline-3-dithiocarboxylate (II) which was further methylated with methyl iodide to 3-bis(methylthio)methylene-1, 4-dioxo-1, 2, 3, 4-tetrahydroisoquinoline (III). Application of alkyl bromoacetate to II, in the presence of potassium carbonate gave 1-alkoxycarbonyl-3-alkoxy-carbonylmethylthio-5-oxo-4H, 5H-thieno[3, 4-c]isoquinolines (IXa, b). II was also derived to dimethyl 6, 11-dioxo-1-methylthio-3, 4, 6, 11-tetrahydro[1, 4]thiazino[4, 3-b]isoquinoline-3, 4-dicarboxylate (X) by the action of dimethyl acetylenedicarboxylate. Treatment of II or III with phosphorus pentasulfide gave 3, 3, 4, 5-tetrahydro-1, 2-dithiolo[4, 3-c]isoquinoline-3, 5-dithione (XI), which the reaction of III with various amines afforded the corresponding amino derivatives (XIII, XIV, and XV). The reaction of III and sodium cyanide gave 3-cyano(methylthio)methylene-1, 4-dioxo-1, 2, 3, 4-tetrahydroisoquinoline (XVII) which reacted with hydrazine hydrate to from 3, 6-dioxo-4-methylthio-2, 3, 5, 6-tetrahydropyri- dazino[4, 3-c]isoquinoline (XVIII).
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KAZUYUKI NAKAGAWA, NANAMI MORAKAMI, SHIRO YOSHIZAKI, MICHIAKI TOMINAGA ...
1974 Volume 94 Issue 5 Pages
613-616
Published: May 25, 1974
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Anti-isoproterenol activity of 51 derivatives of 5-, 6-, 7-, and 8-(3-amino-2-hydroxy)-propoxy-3, 4-dihydrocarbostyril was measured in an anesthetized dog. The derivatives which had 3-tert-butylamino-2-hydroxypropoxy in 5 or 8 position showed a potent activity. Among them, 5-(3-tert-butylamino-2-hydroxy)propoxy-3, 4-dihydrocarbostyril hydrochlo-ride (6) proved to be the most effective. 6 may be the most hopeful compound as an adrenergic β-receptor-blocking agent.
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SHUZO TAKAGI, MASAE YAMAKI
1974 Volume 94 Issue 5 Pages
617-622
Published: May 25, 1974
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From the fresh bulbs of Lycoris sanguinea MAXIM., four known alkaloids, tazettine, haemanthamine, lycoramine, and haemanthidine, were isolated besides lycorine and galanthamine, and found to be identical with the respective authentic specimens. Lycoricidine, lycoricidinol, arolycoricidine, arolycoricidinol, β-sitosterol, methyl linoleate, and an unknown compound N-3, were also isolated. N-3, C
13H
9O
3, N, mp 235°, contains one methyl-enedioxy and one amide groups, but no hydroxyl group. Based on the fact that its dihydro derivative was identical with XIV, N-3 was determined as 4, 5-etheno-8, 9-methylenedioxy-6-phenanthridone (XIII).
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YOSHIO TAKINO, NAOMI SAWANISHI, NOBUHIKO IRITANI
1974 Volume 94 Issue 5 Pages
623-626
Published: May 25, 1974
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Catalytic effect of some kinds of metal ions on the reaction of benzenediazonium sulfate and thiocyanate ion was examined by determination of phenyl thiocyanate produced using gas-liquid chromatography. Catalytic activities of metal ions were as follows : Cu
2+>Cu
+, Fe
2+> Hg
+ > Th
4+> Fe
3+, Bi
3+, Al
3+, Cr
3+, Pb
2+, Cd
2+, UO
22+, Ce
3+, Zn
3+, Co
2+> K
+, Na
+, NH
4+, Mg
2+, Mn
2+, Hg
2+, Ni
2+, Ag
+ > Sn
2+. As a catalyst, Cu
2+, Cu
+, and Fe
2+were found to be more effective than Co
2+ and Fe
3+, which were proposed by Korozynski, et al. The yield of phenyl thiocyanate was better, the larger the amount of thiocyanate ion added. When Cu
2+ was used as a catalyst, the yield of phenyl thiocyanate was increased rapidly until the molar ratio of thiocyanate ion to metal ion became 4, and then slowed down according to the amount of thiocyanate ion. This new method of mixing one mole of benzene-diazonium sulfate, 4 or more mole of potassium thiocyanate, and 1 mole of cupric sulfate in neutral solution and allowing them to react is recommended for synthesis of phenyl thiocyanate, which is obtained in ca. 30% yield by this procedure.
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TETSUZO KATO, YUTAKA YAMAMOTO, SHIRO TAKEDA
1974 Volume 94 Issue 5 Pages
627-632
Published: May 25, 1974
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The reaction of chloroketene diethylacetal (I) with heterocyclic primary amines was studied. Reaction of aniline (IIa) with I afforded ethyl N-phenylchloracetimidate (III) in a good yield. However, 2-aminopyridine (IIb) and 2-aminoquinoline (IIc) reacted with I to give imidazo[1, 2-a]pyridine derivatives (IV, V, and VI) and imidazo[1, 2-a]quinoline derivatives (XI, XII, XIII, and XIV), respectively. On the other hand, reaction of 2-aminothiazole (IId) and 2-aminopyrimidine (IIe) with I afforded 2-chloro-1, 1-diethoxy-ethylamine derivatives (XVIII, XXI), which were easily converted to the corresponding iminoether derivatives (XIX and XXII), respectively.
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TSUNETOSHI KAITO, KAZUHIKO SAGARA, TSUGUCHIKA YOSHIDA, YUJI ITO
1974 Volume 94 Issue 5 Pages
633-638
Published: May 25, 1974
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Fluorometric determination of acetaminophen (I) was studied and a recommended procedure was established. When I was oxidized with K
3Fe(CN)
6 in a slightly alkaline solution, a blue violet fluorescence developed and its intensity was increased by the addition of dimethylformamide. The fluorescent substance exhibited an absorption maximum at 303 mμ in ethanol which could not be observed in I, and it was considered that this absorption is closely related to fluorescence. Its chemical structure was found to be 2, 2'-dihydroxy-5, 5'-diacetylaminobiphenyl from its analytical data. The analytical procedure was as follows : To 1 ml of I solution (20 μg/ml), 2ml of 0.2 M H
3BO
3-KCl-Na
2CO
3 buffer solution (pH 8.5) was added, the mixture was cooled to 0°, and 1 ml of 0.05% K
3Fe(CN)
6 solution was added. After further standing for 5 min at 0°, 2 ml of 0.25% ascorbic acid solution and 5 ml of dimethylformamide were added and fluorescence intensity of the solution was measured at 425 nm, exciting at 337 nm.
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TSUNETOSHI KAITO, KAZUHIKO SAGARA
1974 Volume 94 Issue 5 Pages
639-644
Published: May 25, 1974
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A fluorometric method was examined for the determination of acetamiophen (I) in pharmaceutical preparations. I was hydrolyzed with HCl to produce p-aminophenol (II) which was reacted with benzylamine (III) at 75°in alkaline solution to give a fluorescent substance. Based on these reactions, indirect fluorometric determination of I was established. II was also determined without any interference of I at 20° even if 1000 times its amount of I was added. The analytical procedure for I in pharmaceutical preparations was as follows : To 5 ml of 0.1 N NaOH solution containing 50 mg of I, 5 ml of HCl was added and the solution was boiled for 60 min. The solution was cooled to room temperature and diluted to 2 μg/ml with water. To 1 ml of this solution, 1 ml of 0.1 N NH
4OH-NH
4Cl buffer solution (pH 10.5) and 1 ml of 5% III-HCl solution (adjusted to pH 10.5 with 2 N KOH) were added, and the mixture was heated for 90 min at 75°. After cooling, 1 ml of 0.5 N KOH was added, and diluted to 20 ml with dimethylformamide. The fluorescence intensity of the solution was measured at 490 nm, exciting at 350 nm.
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SHIN MATSUURA, TOSHINOBU KUNII
1974 Volume 94 Issue 5 Pages
645-647
Published: May 25, 1974
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Oxidation of 2'-hydroxy-4-benzyloxy-4', 5', 6'-trimethoxychalcone or 4'-benzoyloxy- 5, 6, 7-trimethoxyflavanone with selenium oxide gave 4'-benzyloxy-5, 6, 7-trimethoxyflavone which, after debenzylation, was partially demethylated with aluminum chloride to give 4', 5- dihydroxy-6, 7-dimethoxyflavone (cirsimaritin).
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TSUYOSHI TOMIMORI, MASAO YOSHIZAKI, TSUNEO NAMBA
1974 Volume 94 Issue 5 Pages
647-651
Published: May 25, 1974
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The xanthone constituents were examined in four kinds of the Nepalese species of Swertia (Gentianaceae), i.e., S. racemosa, S.nervosa, S.gracilescens, and S.dilatata. Norswertianin (I), swertianin (II), methylswertianin (III), gentiacaulein (IV), decussatin (V), desmethylbellidifolin (VI), bellidifolin (VII), and methylbellidifolin (VIII) were isolated and identified, together with oleanolic acid. Distribution of these xanthones are listed.
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HARUSHIGE FUJITA, MASATARO YAMASHITA
1974 Volume 94 Issue 5 Pages
652-654
Published: May 25, 1974
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To elucidate the constituents of the essential oil from the leaves of Citrus depressa HAYATA, the plant growing in Amamioshima (Kagoshima Prefecture) was collected and the essential oil obtained by steam distillation of the leaves was separated into three fractions (neutral, phenolic, and carboxylic acid). These fractions were examined by gas-liquid chromatography, infrared and nuclear magnetic resonance spectroscopy, and 24 kinds of compound (3-hexen-1-ol, thymol, palmitic acid, etc.) were newly detected, besides the known seven compounds (γ-terpinene, etc.).
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