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Volume 83, Issue 3
Displaying 1-25 of 25 articles from this issue
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Identification and Separation of Narcotics by Using Ammonium ReineckateMinoru Yoshimura, Mitsuo Deki, Hisao Tsukamoto1963 Volume 83 Issue 3 Pages 223-226
Published: March 25, 1963
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSDevelopment of the reineckates of alkaloid on a filter paper treated with 5% ammonium sulfate solution results in movement of the alkaloids as free bases. Use of water-saturated butanol-acetic acid (10:1) as the developer gave good separation. Identification was made by cutting out the corresponding parts of the chromatogram, extraction with chloroform, precipitated as reineckates, and by measurement of infrared absorption spectrum. This method was applied to some preparations.View full abstractDownload PDF (505K) -
Colorimetric Determinations of Isonicotinic Acid Hydrazide and 2, 3-Dichloro-α-naphthoquinoneMasami Akatsuka1963 Volume 83 Issue 3 Pages 227-233
Published: March 25, 1963
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSColoration reaction of acid hydrazides and amine compounds with α- and β-naphthoquinones and their derivatives in alkaline state was examined and it was found that a blue coloration occurred between acid hydrazides and α-naphthoquinone derivatives and a red coloration between acid hydrazides and β-naphthoquinone derivatives. Based on this coloration, colorimetric determination of INAH with 2, 3-dichloro-α-naphthoquinone was devised, to be carried out in the following manner.
One cc. each of 0.03% ethanolic solution of 2, 3-dichloro-α-naphthoquinone and 0.1% potassium carbonate solution are added to 3cc. of aqueous solution of INAH, containing 1-10γ/cc., the mixture is allowed to stand for 10 minutes, and its optical density is measured at 620mμ. The content of INAH is calculated from the calibration curve.
Determination of INAH by this method, in the presence of Thioacetazone, pyrazinamide, PAS, and sulfanilamide showed that these substances did not affect its optical density and it is believed that 2, 3-dichloro-α-naphthoquinone is a reagent which might replace sodium β-naphthoquinone-4-sulfonate.
The foregoing process was reversed to carry out the colorimetric determination fo 2, 3-dichloro-α-naphthoquinone (Dichlone) with INAH, which is carried out in the following manner.
To 4cc. of methanolic solution of 2, 3-dichloro-α-naphthoquinone, containing up to 25γ/cc., 0.5cc. each of 0.3% aqueous solution of INAH and 0.1% potassium carbonate solution are added, the mixture is allowed to stand for 10 minutes, and its optical density is measured at 620mμ. The content is calculated from the calibration curve. This colorimetric determination was found to be possible in the presence of chloranil, used as an agricultural chemical in the same way as Dichlone. Although ethyl cyanoacetate, the coloration reagent for Dichlone and chloranil, can be used to determine either one alone, it cannot determine each in a mixture of Dichlone and chloranil.View full abstractDownload PDF (906K) -
Goro Kobayashi, Yoshikata Kuwayama, Shimako Okamura1963 Volume 83 Issue 3 Pages 234-239
Published: March 25, 1963
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSFour oxidation products were isolated from the reaction mixture of 4-methyl-2, 3-dihydrothieno[3, 2-c]quinoline (I) and phthalic monoperacid by alumina chromatography. On the basis of their melting points, elemental analyses, infrared spectra etc. they were revealed to be S-oxide (III), S, S-dioxide (IV), N, S-dioxide (V) and N, S, S-trioxide (VI). Ring closure of 2-methyl-3(2-chloroethyl)-4-chloroquinoline N-oxide (VIII) with sodium bisulfide or thiourea afforded 4-methyl-2, 3-dihydrothieno[3, 2-c]quinoline N-oxide (IX). Heating of III in acetic anhydride gave 4-methylthieno[3, 2-c]quinoline (VII). The reaction product of VII with phthalic monoperacid is presumed to be 4-methylthieno-[3, 2-c]quinoline N-oxide (XV) on the basis of its infrared and ultraviolet spectra and in this case neither dioxide nor trioxide was obtained. Treatment of 2, 3-dihydrothieno-[2, 3-b]quinoline (II) with phthalic monoperacid gave S-oxide (XII) and S, S-dioxide (XIII). The reaction of XII with acetic anhydride afforded thieno[2, 3-b]quinoline (XIV), which was converted into N-oxide (XVI) by means of phthalic monoperacid.View full abstractDownload PDF (930K) -
Preparation of cis- and trans-3-(5-Nitro-2-furyl)acrylic Acid and 2-Alkyl-3-(5-nitro-2-furyl)acrylic Acids by Perkin ReactionHaruo Saikachi, Akira Tanaka1963 Volume 83 Issue 3 Pages 240-244
Published: March 25, 1963
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSNitration of cis- and trans-3-(2-furyl)acrylic acid afforded corresponding cis- and trans-isomers of 3-(5-nitro-2-furyl)acrylic acid, which were also obtained by the decarboxylation of (5-nitrofurfurylidene)malonic acid. On the other hand, by Perkin reaction, 2-methyl-3-(5-nitro-2-furyl)acrylic acid and 2-ethyl-3-(5-nitro-2-furyl)acrylic acid were synthesized from 5-nitro-furfural with potassium propionate and potassium butylate.View full abstractDownload PDF (770K) -
Effect of pH on the Adsorption of Amines from Aqueous Solutions. (1)Akinobu Otsuka, Yoko Chikushi1963 Volume 83 Issue 3 Pages 244-248
Published: March 25, 1963
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSThe influence of pH in liquid phase upon the adsorption of amines by synthetic aluminium silicate gel from water solution has been investigated. The results are:
1) Such an adsorbed amine as 1-ethylpiperidine, quinine, papaverine, pyridine and quinoline was tested by using the sample gel of having about 0.3:1 atomic ratio of Al:Si in the range of pH 2 to 8. The value, i.e. the adsorbed amount per 1 gram of gel was divided by the amine cation equilibrium concentration in liquid phase, was minimum at a pH of 4 and the amount of adsorption increased as the pH dropped at less than 4, having its maximum at around pH 3.
2) At a pH 4 and above, the amount of adsorption increased remarkably, as the pH rose. When the relationship between the amount of adsorption, x/g, and the pH of liquid phase was examined, employing 1-ethylpiperidine, in spite of the original amine concentration, c0, weight of gel, g, and the volume, v, it accorded with the following formula, log x/g/c(b-x/g)=(1-n)pH+logkK where c is the amine cation equilibrium concentration, b the saturated amount of adsorption at pH 7 and n, k and K are the constant.
3) The adsorption isotherm at pH 7 become the Langmuir type, and the value b, calculated from the Langmuir equation was coincided well with the experimental value.View full abstractDownload PDF (612K) -
Effect of pH on the Adsorption of Amines from Aqueous Solutions. (2)Akinobu Otsuka, Shoji Bo, Yoko Chikushi1963 Volume 83 Issue 3 Pages 248-250
Published: March 25, 1963
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSThe adsorption of N-ethylpiperidine from water solution by some sorts of synthetic aluminium silicate gels having a variety of alumina has been examined in the range of pH 2 to 5 in liquid phase and the results obtained are as follows:
(a) The remarkable phenomenon of showing the maximum of the amount of adsorption observed with the sample of having a larger amount of alumina at a pH of around 3, was dubious with the sample of having smaller amount of alumina.
(b) As to the acid treated samples beforehand, the maximum in the phenomenon became not clear, as the condition of the treatment became stronger.
Considering from these results, in the case of adsorption of amines from the water solution, the abnormal phenomenon observed in the range of pH 4 and less, was assumed to be caused by the change over the surface of gel, accompanied by the dissolution of aluminium hydroxide which was present in the gel.View full abstractDownload PDF (401K) -
Koji Kuroda, Masayuki Nakagaki1963 Volume 83 Issue 3 Pages 250-256
Published: March 25, 1963
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSRegarding to the spot on the saturation curve in Fig. 1, the reciprocal humidity, H, of the solution and the molar fraction, x1, of water were measured. The relative equation (3) was found to be formed experimentally, when the relation of the activity coefficient, f1, of water, which was calculated from equation (1), was examined with the mixed ratio, y, of the solute, derived from equation (2), provided that the k of the equation (3) is the smaller one between f1a and f1b. The CRH (Hc), calculated from (3), coincided with the actual value better than with the one calculated from the Eider equation (5).
There are some system which do not accord with the equation (3), therefore the S2-S3 curve was calculated on the two cases where two kinds of solvent coexist and thus three areas A, B and C bounded by were considered in Fig. 5. As to the mixture which is in accordance with equation (3) the actual S2-S3 curve is present in A and B area, and the other mixture which does not accord with the equation (3) is in the C area, being afar outward from the boarder line. In this case, the equation (4) was also inapplicable.View full abstractDownload PDF (896K) -
Koji Kuroda, Masayuki Nakagaki1963 Volume 83 Issue 3 Pages 256-259
Published: March 25, 1963
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSThe experimental equation (5) which was derived from the relative formula (3) x1c (x1a, x1b), in the previous report, whose x1 was replaced by H, is widely applied and coincided well with the actual value better than with that of Elder equation (6).
Employing the x1c (x1a, x1b) formula, the validity of the equation (6) was examined. It was found that the mixture which holds the equation (5) is in A and B area in Fig. 1, and that the one which accords with the (6) present only in the B area. For the mixture which is in C area and is afar outside from the boarder line (2), any equation was inapplicable.
As it is informed in the previous report, equation (1) coincided well with the actual value than with (5), and the equation (1) gives more exact value of CRH, if x1c is known, but the CRH may be estimated roughly from equation (5), if x1c is unknown.View full abstractDownload PDF (514K) -
Inhibition of Isoniazid Acetylation by p-Aminobenzaldehyde and its Related CompoundsKiichiro Kakemi, Takaichi Arita, Hitoshi Sezaki, Masaahiro Nakano1963 Volume 83 Issue 3 Pages 260-263
Published: March 25, 1963
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSMost of isonicotinic acid hydrazide (INAH), given orally to men, undergoes change in vivo and is excreted into urine as acetyl-INAH. It was therefore assumed that inhibition of biological change of INAH might prolong the effect of INAH and examinations were made on compounds which might inhibit acetylation of INAH in a rat. Separatory determination of INAH metabolites in rat urine followed the modification of the process using ion-exchange resin reported in the preceding paper. It was thereby found that none of the compounds examined to date in vitro had any effect except p-aminobenzoic acid (PABA), and that the main metabolites of PABA and esters of PABA had only a weak effect. In connection with PABA, effect of p-aminobenzaldehyde, 4′-aminoacetophenone, their oximes, and semicarbazone and thiosemicarbazone of p-aminobezaldehyde were examined and these were found to be very effective in inhibiting acetylation of INAH. Similar results were obtained with rabbit.View full abstractDownload PDF (674K) -
Determination of Tetracycline in UrineKiichiro Kakemi, Takaichi Arita, Hitoshi Sezaki, Tanekazu Nadai1963 Volume 83 Issue 3 Pages 264-267
Published: March 25, 1963
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSA method for determining urinary concentration of tetracycline was devised by the combination of Permutit column with p-nitrobenzenediazonium chloride reagent. The sample urine is passed through a column of Permutit acidified with hydrochloric acid to adsorb tetracycline on Permutit, this is desorbed with sodium hydroxide solution, and the effluent solution is neutralized. The neutralized solution is colored with p-nitrobenzenediazonium chloride reagent and the amount of tetracycline in the sample urine is determined. Amount of tetracycline excreted into urine was determined by this method after administration of various kinds of tetracycline preparation and it was found that 30-40% is excreted into urine 24 hours after administration. At the same time, biological half-life period of tetracycline was examined and was found to be about eight hours.View full abstractDownload PDF (580K) -
Reaction of Diketene with QuinolineTetsuzo Kato, Tsunehiro Kitakawa, Yutaka Yamamoto1963 Volume 83 Issue 3 Pages 267-271
Published: March 25, 1963
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSReaction of quinoline with diketene afforded C17H13O3N (II) which was transformed into dehydro-derivative C17H11O3N (III) and dihydro-derivative C17H15O3N (IV) by a disproportionating reaction. Hydrolysis of III with potassium hydroxide gave C17H13O4N (VII) and C15H11O3N (VIII). III was reobtained by treatment of VII with conc. hydrochloric acid. Reaction of III with liquid ammonia afforded C17H12O2N2 (V). The above reactions can be explained by suggesting the formula (IIa or IIb) for II which is in accordance with a structure proposed by Berson to a Wollenberg-compound prepared from pyridine and ketene.View full abstractDownload PDF (758K) -
Structure of Leonurine. (3)Yoshimitsu Hayashi1963 Volume 83 Issue 3 Pages 271-274
Published: March 25, 1963
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSThe chemical structure of leonurine was assumed as formula (I). Compound listed in Table 1 were synthesized and their various properties were compared with those of leonurine. As a result, the compound (V) had pKa′ of around 7.0 and the structure of leonurine was proved not to be 1-syringoyl-3-(4-hydroxybutyl)guanidine (V:R=H, n=4).View full abstractDownload PDF (584K) -
On the Permeabilities through Bovine Eye Lens CapsuleMasayuki Nakagaki, Naofumi Koga, Shuzo Iwata1963 Volume 83 Issue 3 Pages 275-278
Published: March 25, 1963
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSIn order to investigate a mechanism of permeability of phenoxazone compounds through membrane, the permeability was examined in this report using the bovine eye lens capsule, though the Visking cellulose membrane was employed in the previous report.
Though the permeability constant (P) of sodium chloride, potassium chloride and all of the pigments inclined to become greater as the temperature rose, the ratio, P/D, of the permeability constant to the diffusion constant (D) in aqueous solution, i.e. the apparent membrane constant (f*), showed its maximum at 25° and it decreased rapidly at 37°. The f* value of the phenoxazone compounds was greater than that of inorganic salts at any temperature. Among the phenoxazone compounds, the order was found to be xanthommatin>C-catalin>A-catalin>catalin.View full abstractDownload PDF (623K) -
Membrane-Constants of Bovine Eye Lens Capsule and the Effects of Phenoxazone Compounds on themMasayuki Nakagaki, Naofumi Koga, Shuzo Iwata1963 Volume 83 Issue 3 Pages 279-282
Published: March 25, 1963
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSThe apparent membrane constant f* was measured employing the Bovine eye lens capsule and the value of f* was observed to decrease in the lapse of permeation period, in the case of permeation of inorganic electrolytes, e. g., sodium chloride and also the influence of phenoxazone compounds to capsule was examined. The results are:
1) When sodium chloride was employed for the permeation of the membrane, the value of f* decreased rapidly within 1-2 hours and it became constant in 4-6 hours.
2) When the capsule was dipped beforehand in catalin solution, one of the phenoxazone compounds, and the permeation was carried out with sodium chloride solution, the value of f* decreased but the value of the velocity constant of membrane aging (k) become smaller, compared with the case of 1).
3) After the treatment with catalin and C-catalin for 1, 2, 4 and 6 hours, two hours' permeation with sodium chloride solution was carried out. The values of f* became greater as the permeation period was longer but any difference of the value has not been found with the sample pre-treated for more than 4 hours.View full abstractDownload PDF (598K) -
The Structures of Trilobine and Isotrilobine. (13). IsotrilobineYasuo Inubushi, Kei-ichi Nomura, Midori Miyawaki1963 Volume 83 Issue 3 Pages 282-288
Published: March 25, 1963
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSBased on the fundamental experiments carried out on simple dibenzo-p-dioxin derivatives, fission reaction with metallic sodium in liquid ammonia was applied to isotrilobine and this base was successfully cleaved into two coclaurine moieties constituting this molecule. Two-step cleavage reaction with metallic sodium in liquid ammonia afforded only one kind of non-phenolic base, S (+)-1-(p-methoxybenzyl)-2-methyl-6-methoxy-1, 2, 3, 4-tetrahydroisoquinoline (XIa). The phenolic base was methylated and afforded S (+)-N, O, O-trimethylcoclaurine (XIV) and (+)-1-(p-methoxybenzyl)-2-methyl-6, 8-dimethoxy-1, 2, 3, 4-tetrahydroisoquinoline (VIII). These experimenal results revealed that isotrilobine is indicated by the structural formula (XV) in which the absolute configuration of the asymmetric centers is both in S configuration.View full abstractDownload PDF (1275K) -
The Structures of Trilobine and Isotrilobine. (14). TrilobineYasuo Inubushi, Kei-ichi Nomura1963 Volume 83 Issue 3 Pages 288-292
Published: March 25, 1963
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSThe structure of trilobine had been believed to be I formula. In order to determine the absolute configuration of its asymmetric centers and the position of its secondary nitrogen, trilobine was N-acetylated and N-acetyltrilobine (IV) was submitted to the improved cleavage reaction with sodium-sodium hydride in liquid ammonia. Two-step fission successfully afforded two coclaurine moieties constituting the trilobine molecule. The non-phenolic base afforded 1-(p-methoxybenzyl)-2-methyl-6-methoxy-1, 2, 3, 4-tetrahydroisoquinoline (V), m.p. 58-62°, [α]D20+128.7° (c=0.633, 95% EtOH). Non-basic phenol was O-methylated and gave 1-(p-methoxybenzyl)-2-acetyl-6, 8-dimethoxy-1, 2, 3, 4-tetrahydroisoquinoline (VI), m.p. 137-142°. From these experimental results and the fact that N-methyltrilobine and isotrilobine are identical substances, it became clear that the structure of trilobine would be represented by VII.View full abstractDownload PDF (808K) -
Masao Tomita, Kiyoshi Fukagawa1963 Volume 83 Issue 3 Pages 293-297
Published: March 25, 1963
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSCleavage reaction with metallic sodium or lithium in liquid ammonia was carried out on aporphine-type bases, (+)-O, O-dimethylcorytuberine (X) and (+)-glaucine (XIV), and the decomposition products were examined.
The starting compound, O, O-dimethylcorytuberine (X) was prepared by derivation of the quaternary base, magnoflorine iodide (IX) to its O, O-dimethyl compound and to the tertiary base (X) by the ethanolamine method. Glaucine (XIV) was also derived from the quaternary base, laurifoline iodide (XIII), by application of lithium aluminium hydride to its O, O-dimethyl compound.
Cleavage reaction of O, O-dimethylcorytuberine (X) in ether or tetrahydrofuran, using metallic alkali in liquid ammonia, gave two kinds of decomposition product. One of them was found to be the O-methyl compound of 2-methoxy-10-hydroxyaporphine (VI), obtained by the same cleavage reaction of O-methyldomesticine (V), i.e. 2, 10-dimethoxyaporphine (XI). The other was identified as 2-oxo-10-methoxy-1, 2, 3, 3a, 11b, 11c-hexahydroaporphine (XII).
The same reaction of (+)-glaucine (XIV) under the same conditions as above was found to form the entirely identical 2, 10-dimethoxyaporphine (XI) and the ketone compound (XII), as in the case of O, O-dimethylcorytuberine (X).
From the result of the foregoing experimental evidences, the absolute configuration of the steric structure of the starting bases used for this reaction, magnoflorine (IX), laurifoline (XIII), and O-methyldomesticine (V), can be related to (+)-glaucine (XIV) whose absolute configuration had already been clarified. These bases are now known to take the L-type configuration (S) as does (+)-glaucine.View full abstractDownload PDF (753K) -
Separation of Oligosaccharides and Identification of Disaccharides in Radix GinsengKiyoshi Takiura, Ichiro Nakagawa1963 Volume 83 Issue 3 Pages 298-300
Published: March 25, 1963
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSSeparatory determination of mono- and di-saccharides contained in the aqueous extract of Ginseng radix was carried out. As the monosaccharide, D-fructose and D-glucose were identified, and the total amount of these monosaccharides in the dried radix was 1.5%. Disaccharides were present in 3.3% amount, and sucrose and maltose were separated as crystals and identified as a result of partition column chromatography using powdered cellulose.View full abstractDownload PDF (325K) -
Ginseng Trisaccharides. (1)Kiyoshi Takiura, Ichiro Nakagawa1963 Volume 83 Issue 3 Pages 301-304
Published: March 25, 1963
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSFour kinds of trisaccharide, A, B, C, and D, were found to be present in the aqueous digest solution of Ginseng radix. A and C were isolated in a pure state by carbon column chromatography. A mixture of A, B, and C was hydrolysed with acetic acid to change A and C to a monosaccharide and disaccharide, (respectively), and hardly hydrolyzable B was obtained in a crystalline state. Based on the results of hydrolysis and periodate oxidation, the composition of the trisaccharides A and B was assumed to be respectively G-Fru-Fru and G-G-G. From the melting point, optical rotation, infrared absorption spectrum, RG, and MG, the trisaccharide A was identified as O-α-D-glucopyranosyl-(1→2)-O-β-D-fructofuranosyl-(1→2)-β-D-fractofuranoside (Fig. 2) and B as O-α-D-glucopyranosyl-(1→6)-O-α-D-glucopyranosyl-(1→4)-O-α-D-glucopyranose (Fig. 3).View full abstractDownload PDF (639K) -
Ginseng Trisaccharides. (2)Kiyoshi Takiura, Ichiro Nakagawa1963 Volume 83 Issue 3 Pages 305-308
Published: March 25, 1963
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSExaminations were made on the structure of the amorphous trisaccharide C, [α]D16+98.3°, isolated from the air-dried Radix Ginseng. This saccharide consists of 2 moles of glucose and 1 mole of fructose, is hydrolyzed by invertase into fructose and maltose, and by pancreatin into glucose and sucrose. One mole of this trisaccharide consumes 4 moles of periodate and forms 1 mole of formic acid. Hydrolysis of its undecamethyl derivative affords 4, 6-tetra-O-methyl-D-fructofuranose, 2, 3, 4, 6-tetra-O-methyl-D-glucopyranose, and 2, 3, 6-tri-O-methyl-D-glucopyranose, and these methylated sugars were isolated by silica gel chromatography and identified. These experimental evidences confirmed this trisaccharide C to be α-maltosyl-β-D-fructofuranoside (Chart 1).View full abstractDownload PDF (774K) -
Syntheses of N-Aminopyridinium DerivativesToshihiko Okamoto, Masaaki Hirobe, Chieko Mizushima, Akio Osawa1963 Volume 83 Issue 3 Pages 308-313
Published: March 25, 1963
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSN-Aminopyridinium halide or its derivatives can be converted into ylide-type compounds, N-iminopyridine or its derivatives, by dehydrohalogenation. Among these ylide compounds, N-acyliminopyridine is quite stable. N-Acylimino compounds thus obtained still have a basic character and readily reacted with various alkylating agents to give novel quaternized pyridine compounds, (N-alkylacylamino) pyridinium salts, in a good yield.View full abstractDownload PDF (1116K) -
Pyrazole Derivatives from the Reaction of the 2-Methyl-3, 3-dialkoxypropionitrile or 2-Alkoxymethylenepropionitriles with Hydrazine DerivativesAkira Takamizawa, Sadao Hayashi1963 Volume 83 Issue 3 Pages 313-318
Published: March 25, 1963
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSReaction of 2-methyl-3-ethoxy-3-methoxypropionitrile (I), 2-methoxymethylenepropionitrile (II), or 2-ethoxymethylenepropionitrile (III) and methylhydrazine in ethanol containing conc. hydrochloric acid gives 5-amino-1, 4-dimethylpyrazole (V) and 3-amino-1, 4-dimethylpyrazole (VI) in approximately equal quantities. Further reaction of VI with I, II, or III gives 1, 3, 6-trimethylpyrazolo[1, 5-a]pyrimidin-7(1H)-one (VIII).
Similarly, reaction with hydrazine hydrate gives 4-methyl-5-aminopyrazole (X) which is led to 3, 6-dimethyl-7-aminopyrazolo[1, 5-a]pyrimidine (XI). Hydrolysis of XI followed by methylation gives VIII. On the other hand, methylation of XI gives 3, 4, 6-trimethyl-7-imino-4, 7-dihydropyrazolo[1, 5-a]pyrimidine (XIII), whose hydrolysis affords the 7-one compound (XIV). Reaction of VIII with hydrazine hydrate results in its cleavage into 4-methyl-4-pyrazolin-3-one (IX) and 1, 4-dimethyl-3-aminopyrazole (VI), while XIV undergoes similar cleavage into IX and 4-methyl-5-methylaminopyrazole (XV). These reactions confirm the structure of these compounds. It should be noted that XI has a fairly strong antifebrile and analgesic activity.View full abstractDownload PDF (1064K) -
Reaction of the Alkyl Propionate Derivatives with ArylhydrazinesAkira Takamizawa, Sadao Hayashi1963 Volume 83 Issue 3 Pages 318-322
Published: March 25, 1963
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSReaction of ethyl 2-diethoxyrnethyl-3-ethoxypropionate (I) and ethyl 2-methoxy-methylene-3-ethoxypropionate (II) with arylhydrazines in ethanolic hydrochloric acid afforded ethyl 1-aryl-4-pyrazolecarboxylate (VIa-c), while the same reaction with ethyl 2-(ethoxymethoxymethyl)propionate (III) gave 1-aryl-4-methyl-2-pyrazolin-5-one (IX, XI, XIV). In case of reaction of I and II, from the results of isolation of corresponding amount of aniline to that of VI from the reaction mixture it seems reasonable to assume that pyrazoline derivative (V) would be resulted first which subsequently aromatized into pyrazole with arylhydrazines.View full abstractDownload PDF (861K) -
Nariko Shinriki, Toshio Nambara1963 Volume 83 Issue 3 Pages 322-326
Published: March 25, 1963
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSColorimetric determination of glucuronic acid in the presence of oxidized starch has been studied. A test solution, adjusted to slight alkalinity, is adsorbed on an anion-exchange resin (Amberlite IRA-410, formate form) and glucuronic acid is eluted selectively with 0.5% formic acid. An aliquot of effluent is taken up and estimated colorimetrically by the orcinol method proposed by Brown. The recovery test was examined on samples containing oxidized starch, lactose, and some O-glucuronides, and good results were obtained as shown in Tables I to IV. Application of the present method to milk did not give satisfactory result owing to coprecipitation when deproteinized.View full abstractDownload PDF (679K) -
Ikuo Matsumoto1963 Volume 83 Issue 3 Pages 327-331
Published: March 25, 1963
Released on J-STAGE: February 19, 2010
JOURNAL FREE ACCESSUtilizing 1-nitro-2, 4, 5-trichlorobenzene (I), easily obtainable from the γ-free isomer of BHC, 5-chloro-2, 4-disulfamoylaniline (V) was prepared by the following route. Nucleophilic replacement of (I) with 2 moles of benzyl mercaptan afforded 1-nitro-5-chloro-2, 4-dibenzylthiobenzene (II) in a high yield. Oxidative chlorination to 2, 4-disulfonyl chloride (III) at 40-45° in aqueous acetic acid, followed by ammonolysis gave 1-nitro-5-chloro-2, 4-disulfamoylbenzene (IV), which yielded (V) by the Béchamp reduction. Similar reaction series were used to prepare 5- or 3-substituted 2, 4-disulfamoylanilines, some of which are hardly obtained by direct sulfonation.View full abstractDownload PDF (699K)
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