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NOBORU OBI, MICHIYA KIMURA
1972 Volume 20 Issue 11 Pages
2295-2301
Published: November 25, 1972
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The rate-determining step of the Janovsky reaction of 1, 3, 5-trinitrobenzene with acetone in methanol is not the deprotonating step but the attacking one of acetonate ion. Kinetic and thermodynamic parameters of the formation and the decomposition of the Janovsky complex I are determined and discussed.
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KAZUO TOMITA, MITSUO NAGANO
1972 Volume 20 Issue 11 Pages
2302-2307
Published: November 25, 1972
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Dimethyl trithiocarbonate (4), which was formed as one of by-products in the preparation of α-acetylenyl xanthate (3), was obtained by treating 2-propynyl xanthate (10) or 3-phenyl-2-propynyl xanthate (18) with potassium xanthate (17). The reaction pathway for the formation of 4 from 18 was studied in detail, and the mechanism of the formation of dimethyl trithiocarbonate (4) and other by-products were consequently clarified.
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MITSUO NAGANO, KAZUO TOMITA
1972 Volume 20 Issue 11 Pages
2308-2314
Published: November 25, 1972
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The mechanism of the formation of 4-benzylidene-1, 3-dithiolane-2-thione (19) in the reaction of 4-benzylidene-1, 3-oxathiolane-2-thione (14) with sodium ethyl xanthate (15) became clear by the measurement of the radioactivity of
35S-4-benzylidene-1, 3-dithiolane-2-thione (32), which was synthesized by the treatment of 14 with
35S-sodium ethyl xanthate (29), and that of
35S-4-benzylidene-1, 3-dithiolane-2-one (38) which was obtained by the oxidation of 32 with mercuric acetate.
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MITSURU FURUKAWA, KENZO SHIRAISHI, SEIGORO HAYASHI
1972 Volume 20 Issue 11 Pages
2315-2319
Published: November 25, 1972
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The reaction of sodium benzylthiosulfate with morpholine was investigated and found to proceed through the intermediate of phenylmethanesulfenylmorpholide and then of dibenzyl disulfide. Whole reaction mechanism was also presumed by the several results obtained.
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SHIGEHARU INOUYE
1972 Volume 20 Issue 11 Pages
2320-2330
Published: November 25, 1972
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Mass spectra of the N-salicylidene derivatives of twenty aminosugars and related compounds including mono- and diaminosugars, monoaminoalcohols and diaminocyclitol were studied. The spectra were characterized by the appearance of strong molecular ion peaks, most of them being the base peak. Fragmentation of the N-salicylidene aminosugars was discussed in terms of the structures, in particular, the substituted positions of amino groups, and compared with fragmentation of the parent free aminosugars.
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SHIGEHARU INOUYE
1972 Volume 20 Issue 11 Pages
2331-2347
Published: November 25, 1972
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Mass spectra of the N-salicylidene derivatives of thirteen members of aminoglycosidic antibiotics and the partially degraded compounds containing 2-deoxystreptamine as a common component were measured. The spectra provided easily identifiable molecular ions, and prominent fragment ions that allowed the sequential determination of the constituent units.
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KAZUNOBU HARANO, TANEZO TAGUCHI
1972 Volume 20 Issue 11 Pages
2348-2356
Published: November 25, 1972
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In general, S-alkyl xanthates of 2-alkenol thermally rearranged to the dithiolcarbonates accompanying allylic shift. When a mixture of two xanthates having different S-alkyl and O-alkenyl groups is allowed to rearrange thermally, no crossover products are obtained. A pair of position isomers did not transform to a same product, but to isomeric products with allylic shift respectively. 3-Aryl-substituted allylic xanthates, on the other hand, rearrange to the corresponding dithiolcarbonates without allylic shift. On the basis of these findings, mechanisms of the transformations are discussed.
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KAZUNOBU HARANO, TANEZO TAGUCHI
1972 Volume 20 Issue 11 Pages
2357-2365
Published: November 25, 1972
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S-Methyl xanthates of 2-cyclohexen-1-ol (IV), 3-methyl-2-cyclohexen-1-ol (V) and cis-3, 5-dimethyl-2-cyclohexen-1-ol (VI) transformed to dithiolcarbonates (VIII, IX and X) accompanying allylic shift (S
Ni'). On the other hand, S-methyl xanthate of 3, 5, 5-trimethyl-2-cyclohexen-1-ol (VII) transformed to 3, 5, 5-trimethyl-2-cyclohexenyl methyl dithiolcarbonate (XI), without allylic shift (S
Ni). Of polycyclic system, S-methyl xanthates of ⊿
1, 9-octalin-2-ol (XIII) and ⊿
4-cholesten-3β-ol (XIX) were submitted to pyrolysis and consequently it was found that they decomposed into methylthio derivatives (XVI and XXI) via rearragement to the dithiolcarbonates (XV and XX). In homoallylic system, pyrolysis of S-alkyl xanthates of cholesterol in the presence of phenolic solvent caused the rearrangement to the corresponding dithiolcarbonates with retention of configuration. In each rearrangement reaction, reaction courses are discussed.
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SHIGEHARU INOUYE, TOMOKO SHOMURA, TAKASHI TSURUOKA, SHOJI OMOTO, TARO ...
1972 Volume 20 Issue 11 Pages
2366-2371
Published: November 25, 1972
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M
1 Substance, one of the main metabolites of SF-837, was isolated from the urine of rats, or digested solution of SF-837 with a liver homogenate, and identified as 4"-depropionyl SF-837 by direct comparison. Another major metabolite, M
2 substance was isolated from the bile of rats, and its structure was proposed to be 14-hydroxyl M
1 on the basis of the mass and nuclear magnetic resonance analyses.
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OSAMI AKI, YASUSHI NAKAGAWA, KENZO SIRAKAWA
1972 Volume 20 Issue 11 Pages
2372-2376
Published: November 25, 1972
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2, 1-Benzisoxazole derivatives were converted into 2, 1-benzisothiazoles simply by fusing with phosphorus pentasulfide in imidazole. 1-Alkyl-2, 1-benzisothiazolium salts, prepared by alkylation of 2, 1-benzisothiazoles with trialkyl orthoformates in the presence of Lewis acids, were shown to react with amines to afford 2, 1-benzisothiazoline derivatives and with glycine ethyl ester to form a 1, 4-benzodiazepin-2-one derivative by the extrusion of the sulfur atom.
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EIICHI FUJITA, TETSURO FUJITA, YASUMORI OKADA, SHIGETAKE NAKAMURA, MAS ...
1972 Volume 20 Issue 11 Pages
2377-2383
Published: November 25, 1972
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The structure of isodotricin, a diterpenoid of Isodon trichocarpus and I. japonicus, was determined to be 4 by a chemical conversion from enmein (1). The more detailed investigation on the stereochemistry of C-16 led to a conclusion for the S-configuration, i. e., the structure and absolute configuration of isodotricin was established as shown in formula 21.
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KENTARO HIRAI, TERUYUKI ISHIBA
1972 Volume 20 Issue 11 Pages
2384-2393
Published: November 25, 1972
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A number of simple reactions of N-(1, 3-oxathiol-2-ylidene) ternary iminium salts with active methylene compounds have been studied and are shown to produce thiophene derivatives readily. The reaction intermediates have been isolated and a reaction mechanism is proposed. The cleavage of benzoylthiophenes gave benzoic acid and the thiophenes having no substituents at the C-2 position. Spectroscopic investigation of the thiophene derivatives have shown the effect of 2-dialkylamino group on their spectra.
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MORIO IKEHARA, SEIICHI UESUGI, MAYUMI KOBAYASHI
1972 Volume 20 Issue 11 Pages
2394-2401
Published: November 25, 1972
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Attempt to obtain 8-bromoadenylyl-(3'-5')-8-bromoadenosine (BrApBrA) (III) by the condensation of N
6, O
2', O
3'-tribenzoyl-8-bromoadenosine 3'-phosphate (V) and 2', 3'-O-ethoxymethylidene-8-bromoadenosine (VI) using dicyclohexylcarbodiimide (DCC) gave 8-oxyadenylyl-(3'-5')-8-bromoadenosine (HOApBrA) (VII) after removal of protecting groups. Structure of VII was confirmed by ultraviolet (UV) and circular dichroism (CD) spectra as well as enzymatic hydrolysis. Condensation of N
6, O
5-diacetyl-8-bromoadenosine 2'(3')-phosphate (IVa) and compound VI using diphenylphosphorochloridate gave 2'-5'(X) and 3'-5'(III) isomers of 8-bromoadenylyl-8-bromoadenosine, which were separated and purified by column chromatography, paper electrophoresis and paper chromatography. Structure of compounds X and III was elucidated by optical properties and enzymatic digestions. Hypochromicities of X and III were 14% and 10%, respectively. From the CD spectra of both compounds, a syn-syn, left-handed structure of these dinucleoside monophosphates was predicted.
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HIROYUKI ISHIZONE, SEIICHI SAKUMA, SACHIKO KAWANISHI, JUNZO SHOJI
1972 Volume 20 Issue 11 Pages
2402-2406
Published: November 25, 1972
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The chemical structure of glycoside E (Ia), C
27H
44O
6, mp 239-240°, [α]
22D-69.9°, which was isolated from Bei-Wujiapi (cortex of Periploca sepium BGE.), was established to be ⊿
5-pregnene-3β, 17α, 20α-triol (20)-β-D-canaropyranoside. It is interesting that glycoside E is the second example of the pregnane type glycoside whose sugar moiety links to the C
20-hydroxyl group other than C
3-hydroxyl group of the aglycone.
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ICHITOMO MIWA, YOSHIHIRO TANABE, JUN OKUDA
1972 Volume 20 Issue 11 Pages
2407-2412
Published: November 25, 1972
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The distribution and degradation of β-D-glucose oxidase (from Penicillium amagasa-kiense) intravenously injected into rats and mice are described in detail. The uptake of intravenously injected β-D-glucose oxidase (0.45 mg/kg) by various tissues of rats and mice was followed over a period of 60 hr by determining the enzyme activity with the polarographic oxygen electrode. The highest activity of the tracer enzyme injected into rats was found in the liver. Considerable amount was taken up by the spleen. The activity in the liver and spleen reached a maximum in 1-2 and 4-6 hr, respectively. Any activity was not found in other tissues 40 min after the injection. Activity in blood also disappeared in 40 min and that in the liver and spleen almost entirely disappeared in 60 hr. Only slight differences in the distribution of the enzyme were observed between rats and mice. β-D-Glucose oxidase in the liver of rats and mice was histochemically detected only in the Kupffer cells, but not in the parenchymal cells. The enzyme degradation studies in vitro suggested that the enzyme taken up by the Kupffer cells may be concertedly inactivated by the hydrolytic enzymes in lysosomes of the Kupffer cells and by the pH elevation (above 7.4) in the cell fluid.
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MASAKO NAKAGAWA, TOSHIHIKO SUZUKI, TSUNEO KAWASHIMA, TOHRU HINO
1972 Volume 20 Issue 11 Pages
2413-2417
Published: November 25, 1972
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Benzoyl methionine (4), its methyl ester (9), and methionine have been oxidized with 3-hydroperoxyindolenines (3a and 7) to the corresponding sulfoxides (5, 10, and methionine sulfoxide).
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ITIRO YOSIOKA, TAMIO SUGAWARA, KANAKO IMAI, ISAO KITAGAWA
1972 Volume 20 Issue 11 Pages
2418-2421
Published: November 25, 1972
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Through the application of the soil bacterial hydrolysis method on a mixture of ginsenosides Rb
1, Rb
2, and Rc, an additional evidence on the genuineness of 20 (S)-protopanaxadiol (I) has been provided. In addition, a prosapogenol (termed as compound K) has been isolated as a major hydrolysate and the structure has been assigned as 20-O-β-D-glucopyranosyl-20 (S)-protopanaxadiol (VI).
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TAKASHI TOBE, TOKUHIKO HIGASHI
1972 Volume 20 Issue 11 Pages
2422-2428
Published: November 25, 1972
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It was found that cycloheximide injected into rats inhibited the incorporation of
14C-leucine into catalase in vivo, not affecting the concentration of catalase-synthesizing ribosomes and the amount of nascent catalase. The liver ribosomes of rats given cycloheximide by intraperitoneal injection incorporated less amino acids into catalase than the ribosomes from intact rat liver, when incubated in vitro with normal cell sap. The cell sap preparation from livers of cycloheximide-treated rats was also less active for catalase synthesis, and the activity could not be restored by treatment with Sephadex. It may be concluded that both the ribosomes and the cell sap are impaired by the treatment of rats with cycloheximide. At low concentration, cycloheximide added into the cell-free system inhibited the labeling of soluble catalase, but not that of catalase-synthesizing ribosomes and nascent catalase. The evidence suggests that the low concentration of cycloheximide interferes with the release of completed catalase molecules from the ribosomes without any effect on incorporation of
14C-leucine into nascent catalase. However, at higher concentrations, the labeling of catalase-synthesizing ribosomes and nascent catalase was decreased, as well as that of soluble catalase. A kinetic study also indicated that this antibiotic would inhibit elongation of nascent catalase on the ribosomes. From these findings, it has been concluded that cycloheximide inhibits the termination, the elongation and possibly the initiation in the course of catalase biosynthesis.
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MITSUNORI WASHITAKE, TATEKI YAJIMA, TOSHIO ANMO, TAKAICHI ARITA, RYOHE ...
1972 Volume 20 Issue 11 Pages
2429-2435
Published: November 25, 1972
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1) Time-course of cutaneous reservoir of both salicylic acid and carbinoxamine showed same pattern as those of decreasing from the recirculating solution in the initial time, and the cutaneous reservoir attained to a definite amount after the lapse of a given time. 2) This definite amount reserved was different with the variation of the drug concentration and the pH values in test solution, and increased as increasing of the fraction of the unionized form of both drugs. 3) The amount decreased from test solution was almost negligible at pH 6.0 where the most of both drugs ionized, however, the amount reserved was slightly detected in the skin. 4) The diffusion of drug into the external area of applied skin was negligible, and the drug permeability through the skin was restricted to the applied area. 5) After test solution was removed from the applied area, the disappearance of drug from the cutaneous reservoir was traced quantitatively during 13 days, and it was cleared that considerable amounts of both drugs reserved remained for a long time. 6) Studying on the reservoir part of drugs, it was recognized that the skin surface, particulary the stratum corneum, had a high ability of the drug reservoir.
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KAZUHIRO IMAI, NOBUKO ARIZUMI, MEITAI WANG, SHOHEI YOSHIUE, ZENZO TAMU ...
1972 Volume 20 Issue 11 Pages
2436-2439
Published: November 25, 1972
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Urinary 3, 4-dihydroxyphenylalanine (DOPA) was extracted with alumina after removal of the fatty substances by shaking with ether-benzene (5 : 2), converted to n-butyl ester with n-butanol-HCl (5N) at 100°for 20 min, trifluoroacetylated with trifluoroacetic anhydride in ethyl acetate and determined by gas chromatography using electron capture detector. The overall recoveries of the added DOPA (50, 75, 100, and 150 ng) from urine (2 ml) were 66.0% ±3.55% (n=8). The pressence of DOPA in normal human urine was confirmed by gas chromatographymass spectroscopy.
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HISAKAZU MORI, HARUHIKO YAMAMOTO, TAKAO KWAN
1972 Volume 20 Issue 11 Pages
2440-2444
Published: November 25, 1972
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The carboxylation of carbonyl, nitro, and nitrile compounds has been investigated in a dimethylformamide solution containing potassium phenoxide with special attention to the easiness of the reaction. Kinetic investigations carried out with the carboxylation of cyclohexanone at 0°led us to suggest that the carboxylation is initiated by the formation of a complex between potassium phenoxide and carbon dioxide (2 : 1) and that the transfer of carbon dioxide from the complex to the organic compounds to form carboxylates is the slow step. The latter step seems to be facilitated by the lower pK
a of the organic substrates.
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TADAHIRO TAKEDA, MASAMI FUNATSU, SHOJI SHIBATA, FUMIKO FUKUOKA
1972 Volume 20 Issue 11 Pages
2445-2449
Published: November 25, 1972
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The polysaccharides of some lichens were studied chemically in relation to their host-mediated antitumour activities against sarcoma 180 in mice. A water-insoluble polysaccharide fraction, EP-3, [α]
17D +200°, from Evernia prunastri (L.) ACH. was shown to be an α-glucan containing α(1→3)(1→4) linkages in the ratio of 4 : 1. The cold water-soluble fraction, EP-4, was separated into EP-7, [α]
17D +12°, and EP-6, [α]
17D +164°. The former was shown to be an antitumour active glucan having β (1→3) (1→4) linkages in the ratio of 3 : 1, while the latter was revealed to be an α(1→3) (1→4) glucan (approx, ratio 3 : 2). The properties of these polysaccharides were discussed in comparing with the data of everniin reported by micovic, et al. A polysaccharide AS-3-IS, [α]
14D+176°, isolated from Acroscyphyus sphaerophoroides LEV. giving an intensive blue iodine-colour reaction was shown to be a new type of α-glucan consisting of α(1→3), (1→4) and (1→6) linkages. A cold water-soluble polysaccharide, AS-3-S, was revealed to be a new glycopeptide. The polysacchrides, ASu-2 and ASa-2 isolated from Alectoria sulcata (LEV.) NYL. and A. sarmentosa (ACH.) ACH. were proved to be lichenin, and ASu-3 and ASa-3 were shown to be isolichenin. The host-mediated antitumour activities of the polysaccharide fractions isolated from the above lichen species were tested.
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ITIRO YOSIOKA, TAMIO SUGAWARA, KYOKO YOSHIKAWA, ISAO KITAGAWA
1972 Volume 20 Issue 11 Pages
2450-2453
Published: November 25, 1972
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The soil bacterial hydrolysis method has been applied to two monoterpenoid glucosides, which were isolated from the roots of Scrophularia buergeriana MIQ. and Paeonia albiflora PALLAS. Although some chemical modification of the glucosides were needed beforehand, the microbiological method has been shown to be a useful procedure in the chemical investigation of the monoterpenoid glucosides.
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HIROSHI HIKINO, YASUSHI OHIZUMI, TSUNEMATSU TAKEMOTO
1972 Volume 20 Issue 11 Pages
2454-2458
Published: November 25, 1972
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The absorption, distribution, and excretion of
3H-labelled ecdysterone were studied in mice by means of autoradiographic technique. When administered intraperitoneally, ecdysterone was rapidly and easily absorbed into the blood and distributed to various organs (in particular, in the excretory organs such as the liver, gall bladder, intestine, and kidney) in which the radioactivity reached the maximal levels quite soon. Its clearance from the organs excluding the excretory organs was rather rapid, and the radioactivity specifically accumulated in the liver was gradually transported into the intestinal lumen via the gall bladder which showed the highest and continuous uptake. The glandular secretion of radioactivity into the gastric mucosa also partially contributes to its transportation from the blood to the digestive tract. After oral administration of
3H-ecdysterone, the absorption from the intestine was slow and limited and high radioactivity in the gastrointestinal tract was retained. The liver took up some radioactivity which attained a maximum soon after administration and gradually decreased due to the biliary excretion through the gall bladder in which the radioactivity hit the maximum level about 1 hr after administration and maintained a high level thereafter. Elimination of the administered ecdysterone from the body appears to be fast and its excretion pattern indicates that the excretion in the feces, mostly derived from the biliary excretion, is much more important than that in the urine after both intraperitoneal and oral administration.
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MAHMOUD M. El-MERZABANI, YOSHIO SAKURAI
1972 Volume 20 Issue 11 Pages
2459-2462
Published: November 25, 1972
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Six maleimide derivatives were synthesized and their anticancer activity was studied. They demonstrated toxic rather than cytotoxic effect.
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NAOKI NAMBU, TSUNEJI NAGAI
1972 Volume 20 Issue 11 Pages
2463-2470
Published: November 25, 1972
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The binding of 13 kinds of phenothiazines (PZS) to bovine serum albumin (BSA) was studied as a series of physico-chemical studies of an approach to an understanding of the membrane action of PZS. The data obtained were analyzed by the usual method for nonspecific binding of drug to protein reported by Klotz, et al. The results obtained by two equilibrium dialysis methods correlated well, and also there was found a correlation between equilibrium dialysis methods and gel filtration method. The binding increased with pH. The order of largeness of the effect of ion species was as follows : citrate>succinate>phosphate>acetate. The entropy change of binding was positive. The larger was the hydrophobicity of molecule of PZS with regard to structure, the more increased the amount bound to BSA. These results may suggest that a hydrophobic interaction takes part in the binding. The binding to BSA correlated with the surface activity of PZS, and also increased with the partition coefficient in dodecan/water system, as may suggest that a hydrophobic interaction plays an important role for the binding. There was found no correlation between the binding to BSA and the adsorbability by carbon black, contrary to the case of barbiturates previously reported. PZS of a similar chemical structure showed the correlations between the binding to BSA and the pharmacological activities, as might suggest that PZS of a similar chemical structure act on various interfaces and biological membranes in a similar way.
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YOSHIKO KAMIYA, SHOJI TAKEMURA
1972 Volume 20 Issue 11 Pages
2471-2476
Published: November 25, 1972
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Kinetic studies were made on the reaction of tetrahydrofuran (II) with N, N-dibromobenzenesulfonamide (I) and from the results, the reaction mechanism was proposed. Results on the first stage of the reaction, namely liberation of bromine can be explained by Eq. (2)-(4). I, which is excited by visible light, acts as a sensitizer. It seems that bromine is liberated from I and simultaneously a ylid-like oxonium ion (III) may be formed as a reactive intermediate. Results on the second stage, namely consumption of bromine can be explained by Eq. (9)-(16). The mechanism was found to involve chain processes starting with formation of an oxonium ion (IV) from III, and reaction of IV with bromine.
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HIROMI TERAUCHI, SHOJI TAKEMURA, YOSHIO UENO
1972 Volume 20 Issue 11 Pages
2477-2480
Published: November 25, 1972
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Secondary amines such as diethylamine (II), piperidine (IV), and 2-ethylpiperidine (VI) were allowed to react with N, N-dichlorophenylacetamide (I) to give N, N-diethyl-N'-benzylurea (III), benzylcarbamoylpiperidine (V), and benzylcarbamoyl-2-ethylpiperidine (VII), respectively. Three moles of amines were consumed to complete the reactions, that is, urea derivatives, amine hydrochlorides, and N-chloroamines were produced, simultaneously. The latters were reduced with sodium bisulfite to give amine hydrochlorides. The mechanism of these reaction was also discussed.
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HIDEOMI FUKUDA, KAZUO WATANABE, TSUGUTAKA ITO
1972 Volume 20 Issue 11 Pages
2481-2483
Published: November 25, 1972
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TETSUJI KAMETANI, KAZUO KIGASAWA, MINEHARU HIIRAGI, TOYOHIKO AOYAMA, K ...
1972 Volume 20 Issue 11 Pages
2483-2487
Published: November 25, 1972
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MAKOTO TAKAI, HISASHI YAMAGUCHI, TAMOTSU SAITOH, SHOJI SHIBATA
1972 Volume 20 Issue 11 Pages
2488-2490
Published: November 25, 1972
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MASASHI TOMODA, SATOMI NAKATSUKA
1972 Volume 20 Issue 11 Pages
2491-2495
Published: November 25, 1972
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YOSHIFUMI MAKI, TORU HOSOKAMI, MIKIO SUZUKI
1972 Volume 20 Issue 11 Pages
2495-2497
Published: November 25, 1972
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SHOZO KAMIYA
1972 Volume 20 Issue 11 Pages
2497-2500
Published: November 25, 1972
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ITIRO YOSIOKA, SHIGEYOSHI SAIJOH, JAMESA. WATERS, ISAO KITAGAWA
1972 Volume 20 Issue 11 Pages
2500-2502
Published: November 25, 1972
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ZEN-ICHI HORII, YUTAKA OZAKI, SHIRO YAMAMURA, TAKEFUMI MOMOSE
1972 Volume 20 Issue 11 Pages
2502-2506
Published: November 25, 1972
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KAZUMOTO MIYAHARA, YOSHITERU IDA, TOSHIO KAWASAKI
1972 Volume 20 Issue 11 Pages
2506-2510
Published: November 25, 1972
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