-
TOZO FUJII, TAKASHI NISHITANI
1973 Volume 21 Issue 11 Pages
2349-2358
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Introduction of the purin-6-yl group into oligopeptides IIa-f on the N-terminal nitrogen was effected by treating them with 6-chloropurine in boiling aq. 1-butanol containing triethylamine or in H
2O containing one eq. mole of NaOH at 90°. The yields of the purinylated peptides (IIIa-f) were 8-73%. Similar condensations of 4-chloro-6-methylpyrimidine with IIa and with glycine provided XII and XIII. In alternative synthesis of IIIa, d, e, (purin-6-yl) amino acids IVa and IVb were coupled with ethyl glycinate or glycylglycinate by the dicyclohexylcarbodiimide method, followed by hydrolysis of the resulting esters VIIIa, b, c. Condensation of α-naphthylamine with ethyl N-chloroacetylglycinate and alkaline hydrolysis of the product furnished N-(α-naphthyl)-glycylglycine (X). Next the hydrolyses of dipeptides IIa, b, c, IIIa, b, c, X, and XII in boiling H
2O at various pH's were examined. At pH 7 all dipeptides were practically stable for at least 10 hr, but at pH 13 they were hydrolyzed at various rates. At pH 1 N-substituted dipeptides IIIa, b, c, X, and XII suffered hydrolysis more rapidly than did the parent dipeptides (IIa, b, c). Among the glyoylglycine derivatives, purinyl derivative IIIa was hydrolyzed most rapidly. At pH 4 purinyl derivatives IIIa, b, c only underwent hydrolysis, whereas the other dipeptides remained unchanged even after 10 hr's reflux. In the hydrolyses of the N-purinylated tri-(IIId, e) and tetrapeptides (IIIf) in H
2O at pH 4 and 100° for 5 hr, the N-terminal residues were almost selectively disconnected to the extent of 21-78%. It is suggested that the observed assistance of the purinyl substituent in hydrolytic cleavage of the N-terminal peptide bond is intramolecular in nature.
View full abstract
-
MASAYUKI ONDA, YASUMASA SUGAMA, HIROKAZU YOKOYAMA, FUMI TADA
1973 Volume 21 Issue 11 Pages
2359-2365
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Epoxidation of 1-(p-methoxybenzyl)-2-methyl-1, 2, 3, 4, 5, 6, 7, 8-octahydroisoquinoline (7) affords the two isomeric epoxides (14 and 15). Chemical evidence shows that performic acid exclusively attacks from the cis-side to the 1-substituent. The competitive reactions of 14 and 15 are qualitatively examined by gas chromatographic and thin-layer chromatographic analyses.
View full abstract
-
KANJI MEGURO, HIDEAKA NATSUGARI, HIROYUKI TAWADA, YUTAKA KUWADA
1973 Volume 21 Issue 11 Pages
2366-2374
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Substitution of the amino group of 2-amino-3H-1, 4-benzodiazepines such as 1 and 2 with primary amines and hydroxylamines was investigated and the 2-substituted compounds 3-19, 21 and 37 were synthesized as shown in Table I. In the case of the reaction with hydroxylamine, however, a 2-aminomethylquinazoline 3-oxide (20) was obtained from a 2-amino-and a 2-methylamino-benzodiazepines (1 and 3) in addition to 2-hydroxyamino-1, 4-benzodiazepine (21). This data show that ring opening at the N-4 : C-5 double bond occurred. A similar ring opening in a 2-methylamino-1, 4-benzodiazepine 4-oxide (4) furnished a quinazoline-2-carboxaldehyde oxime 3-oxide (40). The derivatives of 21 and its oxide (37) were prepared as exemplified by the synthesis of oxadiazolo [4, 3-a] [1, 4]-benzodiazepines (25 and 39).
View full abstract
-
KANJI MEGURO, YUTAKA KUWADA
1973 Volume 21 Issue 11 Pages
2375-2381
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
2-Hydrazino-1, 4-benzodiazepine derivatives, III and X, were synthesized from the corresponding 2-amino derivatives Ia and Ib, respectively. It was found, on the other hand, that the reaction of a 2-chloromethylquinazoline 3-oxide (XIII) with hydrazine did not form X but gave a 2-hydroxyamino-1, 4, 5-benzotriazocine (XIV), which, after hydrogenation over Raney nickel, afforded its deoxygenated compound (XV). The structures of these diazepines and the isomeric triazocines were determined on the basis of chemical and physico-chemical behavior. Novel tricyclic compounds, s-triazolo [4, 3-a] [1, 4] benzodiazepines IX and XII were also prepared.
View full abstract
-
KANJI MEGURO, HIROYUKI TAWADA, HIROSHI MIYANO, YOSHIAKI SATO, YUTAKA K ...
1973 Volume 21 Issue 11 Pages
2382-2390
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
A variety of 4H-s-triazolo [4, 3-a] [1, 4] benzodiazepines (VII) which are highly active in central nervous system depression was synthesized with the aim of investigating structure-activity relationships.
View full abstract
-
MITSURU FURUKAWA, SEISHI TSUIJI, YOKO KOJIMA, SEIGORO HAYASHI
1973 Volume 21 Issue 11 Pages
2391-2395
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
The reaction of benzyl phenylmethanethiosulfinate with morpholine was found to give dibenzyl trisulfide together with dibenzyl disulfide, benzaldehyde and N-thiobenzoyl-morpholine and the reaction mechanism was discussed. In the reaction with other secondary amines instead of morpholine, dibenzyl trisulfide was also obtained.
View full abstract
-
MITSUO NAGANO, MICHIKO OSHIGE, TAKASHI MATSUI, JUNZO TOBITSUKA, KOZO O ...
1973 Volume 21 Issue 11 Pages
2396-2407
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
N-Alkoxycarbonylthioureas (A) were reacted with bromine in CHCl
3 to afford sulfur, alkoxycarbonylureas (B), 3, 5-bis (alkoxycarbonylimino)-1, 2, 4-dithiazolidines (C), 3, 5-bis-(alkoxycarbonylamino)-1, 2, 4-thiadiazoles (D), 2-alkoxycarbonyl-5-alkoxycarbonylamino-3-imino-1, 2, 4-thiadiazolines (E) and 3-amino-5-alkoxycarbonylamino-1, 2, 4-thiadiazoles (F). This paper describes in detail on the confirmation of the structures of these reaction products.
View full abstract
-
MITSUO NAGANO, MICHIKO OSHIGE, TAKESHI KINOSHITA, TAKASHI MATSUI, JUNZ ...
1973 Volume 21 Issue 11 Pages
2408-2416
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
N-Alkoxycarbonyl-N'-(2-thiazolyl) thioureas were reacted with some oxidants, such as bromine, benzoyl peroxide, hypobromous acid and N-bromosuccinimide, to afford 2-alkoxycarbonylimino-thiazolo [3, 2-b] thiadiazolines (X). Furthermore, from the reaction mixtures of N-ethoxycarbonyl-N'-(2-thiazolyl) thiourea (12) with bromine in chloroform, N-ethoxycarbonylimino-thiazolo [3, 2-b] thiadiazoline hydrobromide monohydrate (14) was obtained, which was easily dehydrobrominated to form 2-ethoxycarbonylimino-thiazolo-[3, 2-b] thiadiazoline (13) by treatment with large quantities of water. This paper describes particularly in detail about the structures of 13 and 14.
View full abstract
-
KAZUHIKO KITAO, KAZUYOSHI KUBO, TAKASHI MORISHITA, NOBORU YATA, AKIRA ...
1973 Volume 21 Issue 11 Pages
2417-2426
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Absorption of isomeric N
1-heterocyclic sulfonamides was studied from the rat small intestines employing isomeric N-methyl sulfonamides in addition to usual antibacterial sulfonamides. The physicochemical properties of the compounds were studied in reference to their isomeric form in solution. Following Shepherd's method sulfapyridine and sulfathiazole were confirmed to exist as imido form about 84% and 100% respectively in aqueous solution. N
1-methyl derivatives and ring N-methyl derivatives were adopted as a model of amido form and imido form respectively and the differences of their physicochemical properties and absorption characteristics from undissociated molecules of their parent compounds were discussed. Also relations of physicochemical properties and absorption were persuaded following Hansch's method. And absorption rate constant of undissociated form of the compounds under study was likely to be related to partitioning to n-octanol and molecular weight.
View full abstract
-
KOUICHI YOSHIOKA, GIICHI GOTO, KENTARO HIRAGA, TAKUICHI MIKI
1973 Volume 21 Issue 11 Pages
2427-2431
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
The improved method for synthesizing gonanes having the allyl group at C-13 was examined. Potassium salt of 2-ethoxycarbonylmethylcyclopentane-1, 3-dione (I) was choosen as a starting material and the ethoxycarbonylmethyl group was converted into the allyl group after the steroid skeleton was formed.
View full abstract
-
SHOJI KOJIMA
1973 Volume 21 Issue 11 Pages
2432-2437
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
The effect of food on the gastrointestinal absorption of amobarbital was studied in the rats. The presence of food in the gastrointestinal tract decreased significantly the serum level and brain level of amobarbital and reduced the sleeping time induced by the drug. The amounts of amobarbital remaining to be absorbed in the stomach and intestines were determined in fasted and nonfasted rats. Most of the drug unabsorbed was contained in the stomach in both experimental conditions, but the amounts unabsorbed were greater in the nonfasted rats. It was clarified by the in situ experiment that the primary absorption site of amobarbital was the small intestine. Thereafter, it was demonstrated that the presence of food in the gut decreased the pharmacological activity of amobarbital by the decrease of absorption rate based on delayed gastric emptying. Since amobarbital is very rapidly absorbed in the small intestine, the presence of food will not decrease the extent of absorption of the drug.
View full abstract
-
KINZO NAGASAWA, HISAE YOSHIDOME
1973 Volume 21 Issue 11 Pages
2438-2443
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
In the presence of Cu (II) ion, alkyl 8-quinolyl hydrogen phosphates (alkyl=ethyl, cyclohexyl, and benzyl) converted into the corresponding P
1, P
2-disubstituted pyrophosphates with formation of 8-hydroxyquinoline-Cu (II) chelate in anhydrous pyridine. When this reaction was carried out in pyridine containing alcohols (R'=ethyl, amyl, cyclohexyl, and benzyl), corresponding dialkyl hydrogen phosphates (R-R'=ethyl-cyclohexyl, amyl-cyclohexyl, cyclohexyl-benzyl, and ethyl-benzyl) were formed as a sole product. The factors (water content, solvent, metal ion) which affect this metal-catalyzed reaction were examined, and a possible mechanism for the reaction was presented.
View full abstract
-
MITSUNORI WASHITAKE, TATEKI YAJIMA, TOSHIO ANMO, TAKAICHI ARITA, RYOHE ...
1973 Volume 21 Issue 11 Pages
2444-2451
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
1) The percutaneous absorption through the damaged skin lacking stratum corneum greatly increased as compared with those of the intact skin, and the initial absorption pattern which was distinctly recognized in the intact skin almost disappeared in the damaged skin, and the absorption of the durgs occurs by the simple diffusion of a first order rate from the start of the experiment. 2) The absorption of the drugs in the intact skin are almost negligible at pH 6.0 where the most of the drugs ionized, however, in the damaged skin, the absorption of drugs are distinctly found. 3) The amounts of the drugs reserved in the intact skin attained to a definite amount reserved after the lapes of a given time, and are depicted by the plateau pattern. On the other hand, the amount reserved in the damaged skin varied the pattern which has a peak in early time, and the peak of the amount reserved in the skin increased as increasing of the drug concentration of test solution. 4) The amount reserved in the skin and the amount of the drugs decreased from test solution in the damaged skin decreased as decreasing of the fraction of the unionized form of the drugs, and it was recognized that the peak of amount reserved in the skin has a tendency to reach late. 5) After test solution was removed from the applied area, the amounts of both drugs reserved in the damaged skin are almost disappeared within 4 hours, and the ability as a cutaneous reservoir of drugs was missing in the damaged skin.
View full abstract
-
TOSHIO NAMBARA, MASAHIRO ITO, MICHIKO ITO, JUNKO MOHRI, JUNICHI GOTO, ...
1973 Volume 21 Issue 11 Pages
2452-2459
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
In order to determine the precursor role of neutral steroids in the formation of estetrol in man the titled compound was prepared as a substrate by two different routes. First, 17, 17-ethylenedioxy-5α-androst-15-ene-3β, 5-diol (I), readily available by the known method, was employed as a starting material. Transformation into the 15α, 16α-glycol structure was attained by osmium tetroxide oxidation toward the Δ
15 double bond. Dehydration with thionyl chloride provided a mixture of the Δ
4 and Δ
5-3β, 15α, 16α, 17β-tetraols (V), which was in turn led to the 15, 16-acetonide (VI). Oppenaner oxidation followed by removal of the dioxolane group afforded the Δ
4-3-ketosteroid (VIIIa). Alternatively, 3β, 5β-dihydroxyandrost-15-en-17-one ethylene ketal (XIV), derivable from dehydroepiandrosterone in several steps, was similarly converted into androst-4-ene-3β, 15α, 16α, 17β-tetraol (XXa). Selective oxidation of the hydroxylic group at C-3 with N-bromoacetamide provided the desired compound (VIIIa). The latter synthetic route has proved to be more favorable in respect to overall yield.
View full abstract
-
YOSHIFUMI MAKI, TAKASHI MASUGI, TOKIYUKI HIRAMITSU, TARO OGISO
1973 Volume 21 Issue 11 Pages
2460-2465
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
3-Amino-1, 2, 3, 4-tetrahydrocarbazole-3-carboxylic acid (IIa) and its 6-methoxy, benzyloxy and hydroxy derivatives (IIb-d), a new type of cyclic tryptophan analogue, were prepared. The optical resolution of acetamido-(-)-menthyl ester of IIa (XIIc) was achieved. It was found that IIa inhibited α-chymotrypsin competitively and trypsin noncompetitively.
View full abstract
-
YOSHIFUMI MAKI, TAKASHI MASUGI, KOJI OZEKI
1973 Volume 21 Issue 11 Pages
2466-2473
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Conformational analysis of a pair of isomeric alicyclic α-amino acids was made by comparison of relative rates for alkaline hydrolysis of their ethyl esters. It was found that in a sharp contrast with the case of 2-norbornanone, employment of the Strecker and the Bucherer reactions in 2-bornanone resulted in the predominant formation of the corresponding amino acid possessing exo-amino and endo-carboxyl groups. On the basis of this finding, the stereochemical courses of the Strecker and the Bucherer reactions in the synthesis of alicyclic α-amino acid are also discussed.
View full abstract
-
TOSHIO NAMBARA, KAZUTAKE SHIMADA, SATOSHI IWAMURA, MIKIKO MORI, MUNETA ...
1973 Volume 21 Issue 11 Pages
2474-2478
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
In order to clarify the metabolic fate of 17β-hydroxy-17α-methyl-5α-androstano-[3, 2-c] isoxazole, preparation of the titled compounds as its potential metabolites has been undertaken. Treatment of the appropriate 5α-androstan-3-ones (I, XIa, and XIb) with ethyl formate provided the 2-hydroxymethylene derivatives (II, XIIa, and XIIb), which in turn were condensed with hydroxylamine to yield the desired isoxazole fused steroids (IV, XIIIa, and XIIIb), respectively.
View full abstract
-
TETSUYA KONISHI, SHIGEO BABA
1973 Volume 21 Issue 11 Pages
2479-2487
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
The intracellular distribution of vitamin K
1, K
2 (20) and K
3 in the rat liver and heart was studied by sucrose linear density gradient centrifugation and it was revealed that vitamin K
1 and K
2 (20) which have long alkyl side chain at 3-position of their common frame other than K
3 were incorporated in the mitochondria. This result was well consistent with the previous one which was obtained by differential centrifugation method. Further study of their intramitochondrial distribution revealed that they localized in the inner membrane of the mitochondria and some of them in the soluble fraction. Electron microscopic radioautography of
3H-vitamin K
2 (20) was also studied and it was again proved that this homolog had higher affinity to the membranous structure in the liver cell especially to the mitochondrial inner membrane. This high affinity of these homologs to the mitochondria especially to the inner membrane suggests the participation of them in some regulatory process in the mitochondrial function other than blood coagulation protein synthesis.
View full abstract
-
YOSHIO SASAKI, HIDEKO KAWAKI, YUKO OKAZAKI
1973 Volume 21 Issue 11 Pages
2488-2494
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
The induced paramagnetic shift parameters, S values, of simple aliphatic amines and alcohols, and the α-substituted propane and β-substituted ethanol series were measured at a mole ratio of Eu (DPM)
3/ligand in CDCl
3 of below 0.10. The S value is a measure of the equilibrium between the shift reagent and ligand, for which the steric and electronic effects are responsible, and is expressed by the equation, S=A. e-BΔE where ΔE=ΔE
elect+ΔE
steric
View full abstract
-
SHIGERU GOTO, TETSUYA YAMAGATA, OSAMI TSUZUKI, SADAO IGUCHI
1973 Volume 21 Issue 11 Pages
2495-2499
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
The purpose of this study was to determine the gastric emptying pattern of Phenol Red in solution form and to consider the apparent effect of few drugs on the rate of emptying through the pylorus of orally administered Phenol Red using rabbits. It was found that the gastric emptying of Phenol Red was regarded as exponential in form and the gastric response of rabbits was almost unchanged for two months. Aminopyrine delayed considerably the gastric emptying of Phenol Red from kinetical point of view. Caffeine which has increasing effect on human gastric secretion did not affect the rate of emptying of Phenol Red.
View full abstract
-
HARUAKI YAJIMA, KOUKI KITAGAWA, TOMIRO SEGAWA
1973 Volume 21 Issue 11 Pages
2500-2506
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
The undecapeptide amide, H-Arg-Pro-Lys-Pro-Gln-Gln-Phe-Phe-Gly-Leu-Met-NH
2, corresponding to the entire amino acid sequence of substance P, a bovine hypothalamic peptide, was synthesized by the conventional method. This and C-terminal tetra, penta, hexa, hepta and octapeptide amides were submitted for biological assays. Synthetic substance P caused considerable decrease in blood pressure and heart rate in anesthetized rat, but other shorter chain peptides were less active. When contractility on isolated guinea-pig ileum was examined, the heptapeptide amide exhibited much higher activity than synthetic substance P.
View full abstract
-
YOSHIAKI KISO, YOSHIYUKI KAI, HARUAKI YAJIMA
1973 Volume 21 Issue 11 Pages
2507-2510
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
N-Isobutoxycarbonyl-2-isobutoxy-1, 2-dihydroquinoline and two other analogous derivatives, N-isobutoxycarbonyl-2-methoxy-1, 2-dihydroquinoline and N-isobutoxycarbonyl-2-ethoxy-1, 2-dihydroquinoline, have been used as coupling reagents for peptide synthesis.
View full abstract
-
MASASHI TOMODA, SATOMI NAKATSUKA, NORIKO SATOH
1973 Volume 21 Issue 11 Pages
2511-2516
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Controlled acid hydrolysis of odoratan, the mucilage from Polygonatum odoratum DRUCE var. japonicum HARA rhizome, and of falcatan, the mucilage from Polygonatum falcatum A. GRAY rhizome, has led to the isolations of six oligosaccharides. Analysis of components, periodate oxidation, methylation and partial degradation studies provided the evidences that they are O-β-D-glucopyranosyl-(1→4)-D-mannopyranose, O-β-D-mannopyranosyl-(1→4)-D-mannopyranose, O-β-D-mannopyranosyl-(1→4)-D-glucopyranose, O-β-D-mannopyranosyl-(1→4)-O-β-D-glucopyranosyl-(1→4)-D-mannopyranose, O-β-D-mannopyranosyl-(1→4)-O-β-D-mannopyranosyl-(1→4)-D-mannopyranose, and O-β-D-mannopyranosyl-(1→4)-O-β-D-mannopyranosyl-(1→4)-O-β-D-mannopyranosyl-(1→4)-D mannopyranose.
View full abstract
-
TAKASHI TSUCHIYA, HEIHACHIRO ARAI, HIROSHI IGETA
1973 Volume 21 Issue 11 Pages
2517-2520
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Photolysis of 3-azidopyridazine, i.e., tetrazolo [1, 5-b] pyridazine (I) was examined. Unsubstituted and methyl-substituted compounds (Ia-d) afforded 3-cyanocyclopropenes (III). On the other hand, 6-methoxy compound (Ie) gave the triene (IV) and the ethylene (V and VI). These compounds are considered to be formed via the diazo intermediates (VIII) and the carbenes (X).
View full abstract
-
MICHIYA KIMURA, MASAHIKO TOHMA, TSUTOMU TOMITA
1973 Volume 21 Issue 11 Pages
2521-2528
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
The reactions of cholesterol (I) with hydrogen peroxide in the presence of transitionmetal salts were carried out at moderate temperature in an acetonitrile medium. When ferrous or titanous sulphate was employed, 5, 6α-epoxy-5α-cholestan-3β-ol (II) (and/or epimeric β-epoxide, XII), 5α-cholestane-3β, 5, 6β-triol (III), cholest-5-ene-3β, 7α-diol (IV), and cholest-5-ene-3β, 7β-diol (V) were formed in rather poor yields. The radical scavenger, α-tocopherol, inhibited the hydroxylation at the allylic position and thus no formation of IV and V was observed. On the contrary, titanium trichloride-hydrogen peroxide system was found to consume entirely the substrate (I) giving considerable amounts of III and the chlorinated products such as 5, 6β-dichloro-5α-cholestan-3β-ol (VI), 5-chloro-5α-cholestane-3β, 6β-diol (VII), 6β-chloro-5α-cholestane-3β, 5-diol (VIII), and 6α-chloro-5β-cholestane-3β, 5-diol (IX). The epoxides (II and XII) were separated solely as the artifacts from the monochlorides (VII and VIII) through column chromatography on alumina. The yields of III, VI, the mixture of VII and VIII, and of IX were in an approximate ratio of 2 : 1 : 2 : 4.
View full abstract
-
KEIJI KIJIMA, TAKEICHI SAKAGUCHI, YOICHI IITAKA
1973 Volume 21 Issue 11 Pages
2529-2537
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
The structure of Pigment A obtained in the Voges-Proskauer reaction was determined as 2-(4-methyl-2-morpholino-1 H-5-imidazolylmethylidene)-1, 2-dihydro-1-oxonaphthalene, by the X-ray analysis of Pigment A', a heavy atom derivative of Pigment A. Pigment A' crystallizes in the triclinic system, space group P
-1, with unit-cell dimensions a=8.08Å, b=14.63Å, c=7.43Å, α=101.5°, β=97.2°, γ=92.1°, Z=2. The structure was solved by the heavy atom method and refined by the least-squares method to an R value of 0.065.
View full abstract
-
YOSHIMITSU OKAMORI, MASANOBU HAGA, SETSUZO TEJIMA
1973 Volume 21 Issue 11 Pages
2538-2544
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Syntheses of 4'-acetamido-4'-deoxy-α-lactose (12) and 6'-acetamido-6'-deoxy-α-cellobiose (19) are described starting from 1, 6-anhydro-β-cellobiose (1) with seven steps. The sequence of the reaction is as follows. Selective tritylation and successive acetylation of 1 afford 1, 6-anhydro-2, 3, 2', 3', 4'-penta-O-acetyl-6'-O-trityl-β-cellobiose (2), mp 191-192°, [α]
23D -11°, in 45% yield. Detritylation of 2 with hydrogen bromide in acetic acid gives two products, crystalline 1, 6-anhydro-2, 3, 2', 3', 6'-penta-O-acetyl-cellobiose (3) and sirupy 1, 6-anhydro-2, 3, 2', 3', 4'-penta-O-acetyl-β-cellobiose (4), in a yield of approximately the equal amount. Sulfonylation of 3, substitution of the sulfonate with sodium azide, reduction of the azido-group, acetolysis of the 1, 6-anhydro ring, and deacetylation afford 12. In the same manner, 19 is obtained from 4.
View full abstract
-
TOSHIO MIYAZAKI, NAOKO OIKAWA
1973 Volume 21 Issue 11 Pages
2545-2548
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Water-soluble polysaccharide of polyporus (sclerotium of Grifora umbellata (FR.) PILAT) obtained by Cetavlon fractionation of crude polysaccharide is a glucan, [α] D-25.4° (c=1, H
2O). The results of periodate oxidation, Smith-type degradation, and methylation studies indicated that the glucan was branching at C-6 or C-3 position of glucose residue and possessing (1→3)-, (1→4)-, and (1→6)-lnkages.
View full abstract
-
TAMOTSU KOIZUMI, MICHIHIRO UEDA, MASAWO KAKEMI
1973 Volume 21 Issue 11 Pages
2549-2556
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
An iterative least square method for finding the best fit multiexponential equation to observed data is presented. A computer program is written in ALGOL, which permits the routine fitting of pharmacokinetic data. Given a set of data, number of exponential terms and initial estimates for exponential parameters, the computer program automatically proceeds to obtain a least square fit of the data by an iterative adjustment of the values of the parameters. Numerical tests on published data confirm its applicability.
View full abstract
-
TOHORU TATSUHARA, SADAO IGUCHI
1973 Volume 21 Issue 11 Pages
2557-2561
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Ultrasonically irradiated aqueous solution of chondroitin sulfate C was fractionated by the gel filtration method using Sephadex G 200, and the content of glucuronic acid in each fraction was measured. Only one new peak arose from the depolymerized product after irradiation. This new peak did not shift with prolonged irradiation. From these facts, chondroitin sulfate C in an aqueous solution was suggested to have been depolymerized not gradually, but directly into the species of limited molecular weight by ultrasonic irradiation. From the result of gel filtration, K
av values of the original compound and the depolymerized product were found to be 0.08 and 0.24, respectively. The molecular weight estimated from the obtained K
av value was approximately equal to the limited molecular weight which was calculated by the authors' equation presented in the previous paper. The depolymerized product by ultrasonic irradiation can be an enzyme substrate against chondroitinase and chondro-6-sulfatase, like the original sample. It is supposed that the depolymerized product still maintains the characteristics of the original macromolecular compound.
View full abstract
-
MUNEHISA ARISAWA, NAOKATA MORITA, YOSHIKAZU KONDO, TSUNEMATSU TAKEMOTO
1973 Volume 21 Issue 11 Pages
2562-2565
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
Irisxanthone (IV), C
20H
20O
11·H
2O, decomposing over 208° without melting, a new C-glycosylxanthone, has been isolated from the rhizoma of Iris florentina L. (Iridaceae) along with mangiferin. The structure of irisxanthone (IV) has been determined as 2-C-β-D-glucopyranosyl-5-methoxy-1, 3, 6-trihydroxyxanthone by chemical and spectral studies.
View full abstract
-
HARUAKI YAJIMA, KOUKI KITAGAWA, MASAYUKI KUROBE
1973 Volume 21 Issue 11 Pages
2566-2567
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
-
NENOKICHI HIRAO, JUNJI KAWACHI, BOMPEI YASUI
1973 Volume 21 Issue 11 Pages
2569-2571
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS
-
TADAKAZU MURATA, TOHRU SUGAWARA, KIYOSHI UKAWA
1973 Volume 21 Issue 11 Pages
2571-2575
Published: November 25, 1973
Released on J-STAGE: March 31, 2008
JOURNAL
FREE ACCESS