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HISASHI NOGAMI, JUN HASEGAWA, KAZUO NODA
1969 Volume 17 Issue 2 Pages
219-227
Published: February 25, 1969
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The conversion of thiamine from thiamine propyl disulfide was studied in vitro using rat intestine set at a modified Wiseman and Smyth's apparatus. The following conclusions were drawn from the experimental results obtained. 1) It was found that thiamine propyl disulfide was converted to free thiamine in mucosal solution and that propyl disulfide appeared in intestinal tissues during the conversion. 2) The formation of thiamine in mucosal and serosal solutions followed the first order kinetics apparently and were same magnitude. 3) The conversion may be considered as the coupled reactions between chemical and enzymic systems and the participation of glutathione reductase to this conversion was expected.
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HISASHI NOGAMI, JUN HASEGAWA, SHIRO NAKATSUKA, KAZUO NODA
1969 Volume 17 Issue 2 Pages
228-233
Published: February 25, 1969
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The formation of thiamine from disulfide derivatives, i.e., thiamine tetrahydrofurfuryl disulfide, thiamine disulfide, thiamine benzyl disulfide, and thiamine propyl disulfide, was examined by rat intestine using a modified Wiseman-Smyth's apparatus. From the results obtained the following conclusions were drawn. 1) The rate of thiamine formation followed first order kinetics, and the derivatives with the larger rate constant had the larger partition coefficient for an organic solvent. It would mean that the interaction between lipophilic gut wall and the disulfide derivatives was the one of the important factor for the conversion. 2) The temperature effect on the conversion was examined between 27° and 47°. The contribution of chemical reaction and diffusion process was concluded from the apparent activation energy obtained. 3) Since the reduction was observed at both sides of intestine, the reaction mechanism would not relate directly to the absorption site of intestine but the general biological phenomenon which might be observed in other animal tissues.
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HISASHI NOGAMI, JUN HASEGAWA, KAZUO NODA
1969 Volume 17 Issue 2 Pages
234-241
Published: February 25, 1969
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Assuming glutathione (GSH) as the main part of thiol group contributing for thiamine formation in gut wall from disulfide type derivatives, i.e., thiamine propyl disulfide (TPD) and thiamine disulfide (TDS), the reactivity between GSH and TPD or TDS and the characteristics of enzyme system in gut wall was studied. The following conclusions were drawn from the result presented. 1) The rate constant determined at 37° and pH 7.4 was 9.83×10
2 for TPD and GSH, 3.7×10 for GSH and glutathione propyl disulfide, 1.78×10
3 for GSH and TDS, and 3.72×10
3 for GSH and thiamine glutathione disulfide in liter/mole min, respectively. 2) The enzyme preparation was obtained by dialysis of rat gut wall homogenate. The activity was examined under the presence of GSH and NADPH and K
m=6.25×10
-5 M/liter and optimal pH=7.4 were same as that of glutathione reductase from rat liver. 3) The mechanism proposed for thiamine formation in gut lumen confirmed as the coupled system shown by Eq. (1), (2), and (3).
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KIICHIRO KAKEMI, HITOSHI SEZAKI, ETSUKO SUZUKI, MASAHIRO NAKANO
1969 Volume 17 Issue 2 Pages
242-247
Published: February 25, 1969
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A new interative method to study molecular interactions spectrophotometrically in case of two interacting species being present in comparable concentrations was developed and applied to salicylic acid-caffeine interaction to examine the effects of carbon tetrachloride, benzene, isoamyl acetate, and water on the apparent stability constant of salicylic acid-caffeine complex. The results of the present study have indicated (a) that salicylic acid interacts very strongly in the nonpolar solvents presumably by hydrogen bonding, (b) that their interaction is minimal in the moderately polar solvents, and (c) that they interact strongly in aqueous solution. These differences are discussed in terms of the difference in mechanisms of interaction in various solvents. Because the nature of complexes in organic phase is different from that in aqueous phase, complexes themselves are not likely to penetrate through the phase boundary when caffeine and salicylic acid are allowed to partition between the organic and aqueous phase.
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KIICHIRO KAKEMI, TAKAICHI ARITA, RYOHEI HORI, RYOJI KONISHI, KENJI NIS ...
1969 Volume 17 Issue 2 Pages
248-254
Published: February 25, 1969
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In order to examine the fundamental problems concerning the contribution of the binding to the mucosa in the absorption of barbituric acid derivatives from the rat small intestine, some in situ and in vitro experiments were carried out. It was clarified that the accumulation in the small intestine was negligible during the in situ continuous perfusion, and therefore the absorption rate constants computed from the amount decreased in the perfusion solution express almost quantitatively the penetration into the vascular system. The degree of binding to the mucosa determined in vitro was correlated to the absorption characteristics. The importance of the binding process in the absorption was also confirmed by in vitro uptake experiments. The uptake was classified into two processes ; the adsorption on the mucosal surface and the accumulation in the tissue. Of these two processes, the adsorption was ascertained as a determining step in the entire absorption process from the rat small intestine.
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KIICHIRO KAKEMI, TAKAICHI ARITA, RYOHEI HORI, RYOJI KONISHI, KENJI NIS ...
1969 Volume 17 Issue 2 Pages
255-261
Published: February 25, 1969
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Some qualitative discrepancies from the pH-partition theory demonstrated with barbituric acid derivatives previously were examined with various types of drugs and the confirmation of the suggestion that the binding process to the mucosal surface is an important factor of the absorption from the small intestine was made. The absorption of the ionized form of drugs was also interpreted by this binding factor. Furthermore, the dispositions of the small intestine were compared with that of the other parts of the gastrointestinal tract. The effect of the N-methyl configuration on the absorption was also found to persist the importance of the binding process.
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MOTOHIRO NISHIO
1969 Volume 17 Issue 2 Pages
262-273
Published: February 25, 1969
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The magnetic nonequivalences between the ceminal protons of phenyl phenacyl sulfoxides and phenyl benzyl sulfoxides have been measured in a variety of solvents. A clear correlation observed between the electron withdrawal power of substituent and V
A-V
B is discussed by considering the geometry of these protons with respect to the S-O bond. It is suggested that reaction field effects, specific solvent-solute interactions, as well as the electronic character of substituents are responsible for the observed change in magnetic nonequivalence. It is also suggested that, by a careful consideration of solvent effects, it is possible to make an assignment of these protons, a method for which has not hitherto been proposed for acyclic systems.
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MOTOHIRO NISHIO
1969 Volume 17 Issue 2 Pages
274-278
Published: February 25, 1969
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The methylene proton resonances of 3-benzalthiochromanone 1-oxides (III) and 3, 3-dibromothiochromanone 1-oxides (IV) were determined in deuterochloroform and in trifluoroacetic acid. From a consideration of the solvent shift induced from a hydrogen-bond formation, it is concluded that the sulfoxide functions in these compounds prefer the axial configuration. Assignments of methylene signals were made by an examination of long-range coupling and by examining the difference in TFA-induced shifts of these proton resonances. Assignments of individual methylene AB-signals of phenyl phenacyl (I) and phenyl benzyl sulfoxides (II) were also made, based on the above evidences, and it is concluded that the proton which is more sensitive to a substituent change is in the position trans with respect to the S-O group and gauche to the unshared electron pair on sulfur atom. It is also suggested that the conformational preference of the phenyl group which is bonded to the sulfoxide group is responsible for the discrepancy observed in the substituent effect of the methylene chemical shifts in phenyl sulfoxides I and II.
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ITIRO YOSIOKA, TSUTOMU NAKANISHI, ISAO KITAGAWA
1969 Volume 17 Issue 2 Pages
279-290
Published: February 25, 1969
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The structure of leucotylin, one of the major triterpenoids of a lichen Parmelia leucotyliza NYL., has been established as I on the basis of chemical and X-ray crystallographical investigations. It has also been suggested that zeorin, another major triterpenoid of the same lichen, has a similar carbon skeleton as leucotylin but differs at the C
21 orientation as is expressed by II.
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ITIRO YOSIOKA, TSUTOMU NAKANISHI, ISAO KITAGAWA
1969 Volume 17 Issue 2 Pages
291-295
Published: February 25, 1969
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The stereostructure of zeorin, a widely distributed triterpenoid in the lichen family, has been proposed as II in connection with the structure of leucotylin (I). In addition, a questionnaire has been presented concerning to the C
21-side chian configurations of hopane and isohopane frameworks.
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TETSUO KIMURA, YOSHIO BAN
1969 Volume 17 Issue 2 Pages
296-305
Published: February 25, 1969
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There have been synthesized dl-10-desoxy-18, 19-dihydro-15-epi-hunterburnine according to the oxidative cyclization reaction with mercuric acetate, and its structure was determined by nuclear magnetic resonance (NMR) and mass-spectra.
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HARUO SAIKACHI, HARU OGAWA
1969 Volume 17 Issue 2 Pages
306-314
Published: February 25, 1969
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Seven (5-nitro-2-furyl)-methylated polyenals (I, n=2 to 3, n is the number of vinyl or propenyl group) were prepared from aldehyde dimethyl acetal (n=1 and 2) by alternate or repeated condensation with methyl vinyl ether or methyl propenyl ether in the presence of boron trifluoride etherate. Excepting the formation of (5-nitro-2-furyl)-2, 4-dimethyl-2-cis-4-trans-2, 4-pentadienal (V), the chain extension reaction gave higher homologs of methylated polyenal with trans formyl group. The chemical evidence showing V must be above configuration was clearly given by the cyclization of its dimethyl acetal to 1-methoxy-2-(5-nitro-2-furyl)-3, 5-dimethyl-cyclopenta-2, 4-diene. From the van der Waals projection diagram of V, it was suggested that 3-S-cis spatial configuration is more favored than 3-S-trans conformation. Nuclear magnetic resonance (NMR) spectrum of V supported this suggestion from its chemical shift of the proton adjacent to 5-nitrofuran ring. In the presence of HX (X=Cl or Br), V was easily rearranged to five membered conjugated ketone, 2-(5-nitro-2-furyl)-3, 5-dimethyl-cyclopent-2-en-1-one. This acid catalyzed ring closure of the cis dienal is a new type of rearrangement, which promises to have some synthetic utility.
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TAMETO OKANISHI, MASATOSHI TOGAMI
1969 Volume 17 Issue 2 Pages
315-319
Published: February 25, 1969
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A microdetermination method for quantitative analysis of the steroidal sapogenin content of plants was established. The sapogenins possessing slightly different Rf values were separated completely on thin-layer plates according to the method reported by Peereboom and Beekes. Because of the low recovery rate of the sapogenins after extraction procedures the Kieselgel layer containing the sapogenins was directly heated with anisaldehyde, then again heated with phosphoric acid and centrifugated. The absorbances of the clear supernatants were measured at 540mμ. The effect of the Kieselgel on the absorption spectra of the sapogenins was not observed. The recovery curves were linear between 10 and 60 μg.
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SAKAE WADA, SUIICHI TOMIOKA, IKUO MORIGUCHI
1969 Volume 17 Issue 2 Pages
320-323
Published: February 25, 1969
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Binding constant, K, for 23 phenols with bovine serum albumin was evaluated spectrophotometrically utilizing the albumin-induced metachromasia of 2-(4'-hydroxyphenylazo)-benzoic acid. In the binding, electrostatic force seems dominant but hydrophobic binding may not be negligible with 2, 4-dichlorophenol and 2, 4, 5-trichlorophenol. The values of log K generally correlated with pK
a, in vitro bacteriostatic activity against Staphylococcus aureus 209 P, action of uncoupling oxidative phosphorylation at mitochondria, and π-electron-density for the oxygen-atom of phenolic hydroxy group of phenols,
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HIROSHI MITSUHASHI, MASAMICHI FUKUOKA
1969 Volume 17 Issue 2 Pages
324-328
Published: February 25, 1969
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The synthesis of C/D cis 11β, 12β-oxygenated pregnane derivatives from 3β, 12β-diacetoxy-5α, 25D-spirostan-11-one (II) vis dienone (V) is described. Nuclear magnetic resonance studies indicated the possible conformation of the C-ring in C/D-cis pregnane is not a boat but a chair form.
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SEIGORO HAYASHI, MITSURU FURUKAWA, YOKO FUJINO, SHIGEKI YOSHIMATSU
1969 Volume 17 Issue 2 Pages
329-334
Published: February 25, 1969
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In order to synthesize a variety of 4-amino-6-substituted amino-2-substituted symtriazine, 1-substituted biguanide was allowed to react with ethyl chloroacetate to give 4-amino-6-substituted amino-2-chloromethyl-sym-triazine, from which the purpose compounds were derived. The reactions of 4-amino-6-substituted amino-2-chloromethyl-symtriazine with amines and alkylthiols were successfully carried out to give 4-amino-6-substituted amino-2-substituted aminomethyl-sym-triazine and 4-amino-6-substituted amino-2-alkylthiomethyl-sym-triazine, respectively. However, in the reaction with sodium alkanethiosulfonate, it was found to result in the formation of the corresponding sulfone afforded by the partial desulfurization in the intermediately formed 4-amino-6-substituted amino-2-methoxythiosulfonyl-sym-triazine. This sulfone was confirmed to be identical with that obtained by oxidation of the corresponding sulfide. The mercaptylation of 4-amino-6-piperidino-2-chloromethyl-sym-triazine with thiourea was resulted in the formation of the corresponding disulfide rather than the thiol compound anticipated.
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SHUNJI IMAI, TOMOYOSHI TOYOSATO, MICHIHIKO SAKAI, YASUO SATO, SHOJI FU ...
1969 Volume 17 Issue 2 Pages
335-339
Published: February 25, 1969
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1056 species of plants and 351 crude drugs were screened by the Chilo dipping test looking for the phytoecdysones. 13 species of Pteridophyta and 23 species of Gymnospermae and Angiospermae were newly found to show the insect-moulting activity. The chemotaxonomical relations were discussed.
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SHUNJI IMAI, TOMOYOSHI TOYOSATO, MICHIHIKO SAKAI, YASUO SATO, SHOJI FU ...
1969 Volume 17 Issue 2 Pages
340-342
Published: February 25, 1969
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The isolations of the following substances are described : cyasterone and ecdysterone from Ajuga decumbens THUNB., A. incisa MAXIM. and A. nipponensis MAKINO, and ecdysterone from Trillium Smallii MAXIM., T. Tschonoskii MAXIM., Stachyurus praecox SIEB. et Zucc. and Polypodium japonicum MAKINO.
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AKIRA TAKAMIZAWA, SAICHI MATSUMOTO, SHOJI SAKAI
1969 Volume 17 Issue 2 Pages
343-347
Published: February 25, 1969
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Hydroxymethylthiamine, phosphate free "active formaldehyde, " was synthesized by the acid treatment of 2-phenyloxalylthiamine-O, O'-diacetate or 2-α-furyloxalylthiamine-O, O'-diacetate, and on alkaline treatment it was converted into a dimeric 1, 4-oxazine derivative (X) involving a ring expansion and auto-oxidation.
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MORIO IKEHARA, SEIICHI UESUGI
1969 Volume 17 Issue 2 Pages
348-354
Published: February 25, 1969
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Direct bromination of adenine nucleotides was achieved by the use of bromine-water as brominating agent in the alkaline or buffer solution. By this method 8-bromoadenosine 2-', 3'-and 5'-monophosphate, 5'-di- and tri-phosphate, and 3', 5'-cyclic phosphate were synthesized in satisfactory yield. Mechanism of bromination of adenine nucleotides was discussed.
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AKIHIKO ISHIDA, YOSHIRO HIYOSHI, TOSHITAKA KOGA, MUNEMITSU TOMOEDA
1969 Volume 17 Issue 2 Pages
355-360
Published: February 25, 1969
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In connection with characterization of unique ultraviolet absorptions at around 223 and 270 mμ of the 3, 5-dieno [3, 4-b] oxathiano system in the steroid nucleus, cholesta-3, 5-dieno [3, 4-b] oxathiane was reduced with lithium in liquid ammonia to give cholest-3-eno [3, 4-b] oxathiane accompanied by 4α-(β-hydroxyethylthio)-cholest-5-ene, bis (cholest-4-en-4-yl) disulfide, and a mixture of cholest-4-ene and -5-ene. The 3-eno [3, 4-b] oxathiano system thus obtained gave in its ultraviolet spectrum an absorption at 227 mμ. It led to a conclusion that the local conjugation of non-bonding p-electrons of oxygen and sulfur atoms and π electrons of 3-C and 4-C atoms in the conformationally rather fixed 3-eno [3, 4-b] oxathiano system affords a unique ultraviolet absorption in a shorter wave length region than 230 mμ. Origin of characteristic ultraviolet absorptions of the 3, 5-dieno [3, 4-b] dithiano system was analogously deduced.
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TOSHIO MIYAZAKI, TOSHIRO YADOMAE
1969 Volume 17 Issue 2 Pages
361-365
Published: February 25, 1969
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Gradual partial hydrolysis and methylation studies of the intracellular polysaccharide from P. chrysogenum showed that the structural feature is a straight chain and it contains following units : 1) acid-labile 1→5 linked D-galactofuranose residue, 2) smaller amount of 1→3 linked D-galactopyranose residue, 3) O-β-D-mannopyranosyl-(1→3)-D-mannose, [α]
D+11.1°, 4) O-β-or α-D-mannopyranosyl-(1→2 or →3)-O-β- or α-D-mannopyranosyl-(1→3 or →2)-D-mannose, [α]
D+16.6°. The most probable structure of the polysaccharide is discussed.
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KEIJI YOSHIDA, FUMIHIKO WATANABE
1969 Volume 17 Issue 2 Pages
366-374
Published: February 25, 1969
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The possible four isomeric C-1, 2 ketols and diols of 17β-hydroxy-A-nor-5α-androstane were prepared. The rearrangements of the four ketol isomers under acidic and basic conditions were examined.
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TOSHIO NAMBARA, HIROSHI HOSODA, MASAHIRO USUI
1969 Volume 17 Issue 2 Pages
375-380
Published: February 25, 1969
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15α- and 17α-bromo-3β-hydroxy-5α, 13α-androstan-16-one acetates (VI, VII) were synthesized starting from the parent 16-oxosteroid (Ib) by way of the enol acetate (V). Configuration of both bromine atoms introduced was established to be α by the standard method of Fieser and Ettorre. These two positional isomers were readily distinguished by leading to the Δ
15- and Δ
16-unsaturated compounds (X, XI), respectively. On the basis of infrared, ultraviolet, rotatory dispersion and circular dichroism spectral data, the nature of 15α- and 17α-bonds and the conformation of rign D with a ketone at C-16 were discussed.
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HIROAKI NOMURA, TOSHIHIRO ISHIGURO, SHIRO MORIMOTO
1969 Volume 17 Issue 2 Pages
381-386
Published: February 25, 1969
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Phosphorylation of 5, 6-isopropylidene-L-ascorbic acid with phosphorus oxychloride gave mainly a mixture of four phosphates. Column chromatography on Dowex-1-bicarbonate with a solution of sodium bicarbonate as a developer was found suitable for the separation of these phosphates for the preparative purpose. Consequently, L-ascorbic acid 3-phosphate and 3-pyrophosphate were isolated as the magnesium salts. Treatment of the former with diazomethane, followed by successive amidation and ozonization gave methyl oxamate, and this provided evidence that the starting ester was the 3-phosphate. The latter ester, on treatment with acid or alkali, afforded quantitatively the same product, i.e., L-ascorbic acid 3-phosphate. These facts, together with the elemental analysis and potentiometric analysis, determined the structure of the latter to be L-ascorbic acid 3-pyrophosphate.
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HIROAKI NOMURA, TOSHIHIRO ISHIGURO, SHIRO MORIMOTO
1969 Volume 17 Issue 2 Pages
387-393
Published: February 25, 1969
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Phosphorylation of 5, 6-isopropylidene-L-ascorbic acid (I) in acetone with phosphoryl chloride gave, in addition to L-ascorbic acid 3-phosphate (II) and 3-pyrophosphate (III), the following two derivatives, i.e., bis (L-ascorbic acid-3, 3') phosphate (IV) and L-ascorbic acid 2-phosphate (V). The structure of these phosphates was determined on the basis of elemental analysis, potentiometric titration, NMR-analysis, supplemented by studies of the hydrolysis. IV was hydrolyzed by acid and alkali most readily among the four isomers. By being passed through a column of Dowex-1-chloride with 1N hydrochloric acid, this compound quantitatively afforded equimolar amount of II and L-ascorbic acid. On the other hand, during the hydrolysis of V in 0.5N hydrochloric acid at 100°, the phosphoryl migration to II was ob served. On the alkali treatment, V was shown to be stable and no migration was detected.
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IKUO MORIGUCHI, NOBUYOSHI KANENIWA
1969 Volume 17 Issue 2 Pages
394-397
Published: February 25, 1969
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In the production of tablets containing cyanocobalamin, it has been advised to use magnesium stearate as a lubricant because talc adsorbs cyanocobalamin and consequently interferes with intestinal absorption and assay of the vitamin. But magnesium stearate can not always replace talc because of the difference of the lubrication mechanisms. Cyanocobalamin is usually formulated together with other vitamins, especially pyridoxine and thiamine, in the tablets. In this work the adsorption of cyanocobalamin on talc in the presence of pyridoxine and thiamine was studied to obtain some information about employment of talc as a lubricant of such tablets, and the competitive adsorption was treated some what theoretically.
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OSAMU NAGASE, YASUHIRO HOSOKAWA, MASAO SHIMIZU
1969 Volume 17 Issue 2 Pages
398-399
Published: February 25, 1969
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Wieland synthesized 2'-ketopantothenic acid [N-(4-hydroxy-3, 3-dimethyl-2-oxobutyryl)-β-alanine] (Keto-PaA) (V) and reported its uneffectiveness as the growth factor for Streptobacterium plantarum 10 S (=Lactobacillus arabinosus). The keto compound (VI) corresponding to pantethine, 2', 2''-diketopantethine (Keto-PTSS), has not yet been known. It seems very interesting to examine the possibility of enzymatic conversion of these compounds to the corresponding active vitamins in mammalian body. This paper describes the synthesis of these keto compounds.
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HISAO YAMAMOTO, SHIGEHO INABA, MASARU NAKAO, ISAMU MARUYAMA
1969 Volume 17 Issue 2 Pages
400-403
Published: February 25, 1969
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YASUHIKO SHIRASU, YUKO MORITA, YASUO FUJIMOTO, TAKASHI TATSUNO, YOSHIO ...
1969 Volume 17 Issue 2 Pages
406-408
Published: February 25, 1969
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YASUO YURA, JUNYA IDE
1969 Volume 17 Issue 2 Pages
408-410
Published: February 25, 1969
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TOMISHIGE MIZOGUCHI, KEISUKE SHIGEZANE, NORIO TAKAMURA
1969 Volume 17 Issue 2 Pages
411-412
Published: February 25, 1969
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HIROYUKI SATO, TAKENORI TANIMURA, TERUMI NAKAJIMA, ZENZO TAMURA
1969 Volume 17 Issue 2 Pages
413-414
Published: February 25, 1969
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HIROSHI HIKINO, TOMOAKI KOHAMA, TSUNEMATSU TAKEMOTO
1969 Volume 17 Issue 2 Pages
415
Published: February 25, 1969
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KYOICHIA. WATANABE, MICHAELP. KOTICK, JACKJ. FOX
1969 Volume 17 Issue 2 Pages
416-418
Published: February 25, 1969
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