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Den'ichi Mizuno
1964 Volume 84 Issue 9 Pages
787-792
Published: September 25, 1964
Released on J-STAGE: February 19, 2010
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Synthesis and Antimicrobial Activity of 3-(5-Nitro-2-furyl) acryl-Heterocyclic Compounds
Tsutomu Irikura, Kazunari Shirai, Shimao Sato
1964 Volume 84 Issue 9 Pages
793-796
Published: September 25, 1964
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In a search for new antibacterial agents, combination of nitrofuran ring and heterocycle was attempted and over 10 kinds of new derivatives were prepared. An antifungal compound, S-(1-oxido-2-pyridyl)-5-nitro-2-furanthioacrylate, was found by antifungal tests using Trichophyton.
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Syntheses of 1-Phenyl-2 (or 3)-aminoalkanethiol Derivatives
Haruki Nishimura, Hideji Takamatsu
1964 Volume 84 Issue 9 Pages
797-805
Published: September 25, 1964
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Various derivatives (II) of 1-phenyl-2-aminoethanol were obtained by the application of an amine to 2-bromoacetophenone followed by reduction, or by amination of 1-phenyl-2-bromoethanol, and chlorination of II afforded the corresponding 2-chloro-2-phenylethylamine derivatives (III). Application of sodium hydrosulfide, sodium thiosulfate, or thiourea to III gave the corresponding thiosulfonic acid (IV) or isothiuronium salt (V), and treatment of IV with hydrochloric acid or of V with alkali produced 1-phenyl-2-aminoethanethiol derivatives (VI), which were oxidized to the corresponding disulfides (VII). VI was also obtained by the amination of α, β-epithiostyrene (VIII), while desulfurization of IV with Raney nickel gave 2-phenylethylamine derivatives. These experiments proved that the reaction of III to IV and V was not accompanied by rearrangement-substitution. 1-Phenyl-3-alkylaminopropanethiol and its disulfide were synthesized from 1-phenyl-3-alkylaminopropanol in a similar manner.
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Configuration of 1-Phenyl-2-alkylaminopropanethiol. (1)
Haruki Nishimura
1964 Volume 84 Issue 9 Pages
806-811
Published: September 25, 1964
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From the strength of the hydrogen bonding between N and SH in the infrared absorption spectra of (+)- and (-)-1-phenyl-2-dimethylaminopropanethiol (III and III′), obtained by the application of sodium thiosulfate to L-(+)-
threo- and L-(-)-
erythro-N, N-dimethyl-1-chloro-1-phenyl-2-propylamine hydrochlorides (I and I′), followed by hydrolysis, it was assumed that III is the
threo series and III′, the
erythro series. III is also obtained by the application of potassium thioacetate or sodium hydrosulfide to I or by application of thiourea followed by alkali treatment of the isothiuronium salt (V) thereby formed.
Similarly, two kinds of 1-phenyl-2-methylaminopropanethiol (VIII and VIII′) and 2-imino-3, 4-dimethyl-5-phenylthiazolidine (X and X′), derived from L-(+)-
threo- and L-(-)-
erythro-N-methyl-1-chloro-1-phenyl-2-propylamine hydrochloride (VI and VI′) by the application of foregoing reagents, were also determined of their steric configuration in relation to III and III′. These experiments proved that application of nucleophilic reagents to I, I′, VI, and VI′ afforded derivatives without change in their steric configuration.
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Configuration of 1-Phenyl-2-alkylaminopropanethiol. (2). Hofmann Degradation of 1-Phenyl-2-dimethylaminopropanethiol Quaternary Salt
Haruki Nishimura
1964 Volume 84 Issue 9 Pages
811-817
Published: September 25, 1964
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Application of sodium thiosulfate to L-(+)-
threo-N, N-dimethyl-1-chloro-1-phenyl-2-propylamine hydrochloride, followed by hydrolysis gave (+)-1-phenyl-2-dimethylaminopropanethiol (II) which was derived to the quaternary salt (IV or V) and treated with sodium hydroxide to form (+)-1, 2-epithiopropylbenzene (VI′). Treatment of D-(+)-
erythro-1, 2-epoxypropylbenzene (VIII′) with potassium thiocyanate gave L-(-)-
erythro-1, 2-epithiopropylbenzene (IX′), which was found to be the antipode of VI′. It is therefore assumed that VI′ is the D-(+)-
erythro series and II, the L-(+)-
threo series.
(-)-Aminothiol (II′), similarly derived from L-(-)-
erythro-N, N-dimethyl-1-chloro-1-phenyl-2-propylamine hydrochloride (I′) was found to be the L-(-)-
erythro series and that D-(+)-
threo-epithio compound (VI) is derived from it. Steric configuration of VI and VI′ was also determined from their nuclear magnetic resonance spectra. Hofmann degradation of the quaternary salt of 1-phenyl-2-dimethylaminoethanethiol also gave the same result. Epithio compounds (VI and VI′) underwent desulfurization by heating and produced
trans-β-methylstyrene.
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Configurations of N-Alkyl-1-phenyl-2-chloropropylamines and their Rearrangements with Nucleophilic Reagents
Haruki Nishimura
1964 Volume 84 Issue 9 Pages
817-824
Published: September 25, 1964
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Treatment of DL-
erythro-1-methylamino-1-phenyl-2-propanol (V) hydrochloride with phosphorus pentachloride or with thionyl chloride results in the formation of two kinds of N-methyl-1-phenyl-2-chloropropylamine hydrochloride (VI and VI′). Application of sodium thiosulfate to VI and VI′ gave the thiosulfonic acid derivatives (VII and VII′). VII′ obtained from VI′ was found to be DL-
threo-1-phenyl-2-methylaminopropylthiosulfonic acid, and VII obtained from VI was found to be the
erythro compound formed by rearrangement. This result indicates that this reaction proceeds with two Walden inversions via the intermediate aziridinium compound. Actually, treatment of VI and VI′ with sodium hydroxide respectively afforded DL-
threo- and DL-
erythro-1, 2-dimethyl-3-phenylaziridine (XVIII′ and XVIII). This fact shows that VI is the
erythro series and VI′, the
threo series. Application of hydrosulfide or thioacetate to VI and VI′ gave the expected rearrangement products.
The only product, N, N-dimethyl-1-phenyl-2-chloropropylamine hydrochloride (XX), obtained by chlorination of DL-1-dimethylamino-1-phenyl-2-propanol, also afforded the rearranged
erythro compound by application of similar nucleophilic reagents and XX was found to be the
erythro series compound.
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Rearrangements of 1-Phenyl-2-chloroethylamines with Nucleophilic Reagents
Haruki Nishimura
1964 Volume 84 Issue 9 Pages
824-830
Published: September 25, 1964
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Application of nucleophilic reagents, such as alkoxides, sodium hydroxide, sodium thiosulfate, and sodium hydrosulfide, to DL- and D-N, N-dimethyl-1-phenyl-2-chloroethylamine (VI and XIV) gave DL- and L-N, N-dimethyl-1-phenyl-1-(substituted)ethylamines. This reaction showed that there is apparently a steric correlation between the starting. compounds and the products. The same reaction of 1-phenyl-2-chloroethylamine by the application of sodium thiosulfate or sodium hydrosulfide gave the rearrangement products, 1-phenyl-2-aminoethylthiosulfonic acid and 1-phenyl-2-aminoethanethiol. VI and XIV were found to undergo facile rearrangement by heating to DL- and L-N, N-dimethyl-2-chloro-2-phenylethylamines. Based on these results, steric configuration of the optically active N, N-dimethyl-2-chloro(mercapto-, substituted mercapto-, or alkoxy)-2-phenylethylamines was determined.
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Shoji Toyoshima, Satoru Tanaka, Tatsuo Komaki
1964 Volume 84 Issue 9 Pages
830-836
Published: September 25, 1964
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1-Arylsulfonyl-2, 3-dialkyl-2-thiopseudoureas (VI) were synthesized
via 1, 2-dialkyl-2-thiopseudoureas (V) according to the method of Winthrop, and the properties of these V and VI are given in Tables I and II. VI, similar to sulfonylthioureas, undergo desulfurization by silver salt, iron salt, and chromium trioxide to form the corresponding 1-arylsulfonyl-3-alkylureas (VII). Desulfurization of 1-(
p-acetylbenzenesulfonyl)-2-benzyl-3-cyclohexyl-2-thiopseudourea (VI-32), symthesized via
p-acetylbenzenesulfonyl chloride (XII) which obtained by oxidation of
p-ethylbenzenesulfonyl chloride (XI) with chromium trioxide, affords 1-(
p-acetylbenzenesulfonyl)-3-cyclohexylurea (VII-3) but chromium trioxide oxidation of 1-(
p-ethylbenzenesulfonyl)-2-benzyl-3-cyclohexyl-2-thiopseudourea (VI-37) gives VII-3 in one step. Under a mild oxidation condition, 1-(
p-ethylbenzenesulfonyl)-3-cyclohexylurea (VII-4) is formed.
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Color Reaction of Phenols with 1-Nitroso-2-naphthol
Masuo Umeda
1964 Volume 84 Issue 9 Pages
836-838
Published: September 25, 1964
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Coloration of phenols with 1-nitroso-2-naphthol in nitric acid solution was examined. About fifty phenolic compounds were examined and the specificity of
para-substituted phenols to this coloration reported to date does not seem to be necessarily true. This coloration reaction occurs with all phenols having a positive substituent and those with negative substituent hardly undergo this coloration. Specificity of 1-nitroso-2-naphthol to
para-substituted phenols is observed only when the concentration of this reagent is low. This is probably due to the fact that
para-substituted phenols easily undergo nitration with nitric acid and form nitrophenols which do not react with 1-nitroso-2-naphthol. The same coloration occurs with 2-nitroso-1-naphthol and disodium 3-hydroxy-4-nitroso-2, 7-naphthalenedisulfonate, but less readily than with 1-nitroso-2-naphthol. The same coloration reaction was also found to occur with the use of ammonium cerium sulfate in place of nitric acid.
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On the Mechanism of Color Reaction of p-Substituted Phenols with 1-Nitroso-2-naphthol and Nitric Acid
Masuo Umeda
1964 Volume 84 Issue 9 Pages
839-845
Published: September 25, 1964
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Examinations were made on the mechanism of coloration reaction of
para-substituted phenols with 1-nitroso-2-naphthol·nitric acid. The structure of the reaction product was clarified and the mechanism was elucidated.
p-Cresol, 2-naphthol, and 4′-hydroxy-acetanilide were used as the
para-substituted phenol, they were colored by 1-nitroso-2-naphthol in nitric acidity, and extract of the colored solution with ethyl acetate was chromatographed over alumina column. The product thereby obtained were 10-methyl-5
H-benzo [
a] phenoxazin-5-one (I) from
p-cresol, 5
H-dibenzo [
a, j]-phenoxazin-5-one (II) from 2-naphthol, and 10-acetamido-5
H-benzo [
a] phenoxazin-5-one (III) from 4′-hydroxy-acetanilide. Besides III, 10-acetamidobenzo [
a] phenoxazonium nitrate (IV) was also obtained, which is responsible for coloration and easily converted to III in an aqueous solution. It is assumed from these evidences that, in this coloration reaction, condensation of
para-substituted phenols with 1-nitroso-2-naphthol in nitric acidity takes place first to form labile benzo [
a] phenoxazonium nitrate with coloration, and this compound further undergoes oxidation to form the 5
H-benzo [
a] phenoxazin-5-one derivatives.
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Colorimetric Determination of Resorcinol with 1-Nitroso-2-naphthol and Nitric Acid, and its Reaction Mechanism
Masuo Umeda
1964 Volume 84 Issue 9 Pages
846-851
Published: September 25, 1964
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Colorimetric determination of resorcinol with 1-nitroso-2-naphthol in nitric acid solution was established and its reaction mechanism was clarified. Reaction of resorcinol and 1-nitroso-2-naphthol in the presence of nitric acid and a minute quantity of sodium nitrite produces reddish violet color which has absorption maximum at 550mμ. This colored solution was diluted with a large volume of water, extracted with chloroform, and the product was purified by silica column chromatography. The product was found to be 9
H-benzo [
a] phenoxazin-9-one, agreeing with the compound synthesized by another route. It was assumed that this product, formed
via an indophenol compound, colors reddish violet on being dissolved in nitric acid. For the colorimetric determination of resorcinol, the following method is recommended.
One ml. of the sample solution (containing 10-120γ/ml. of resorcinol) is accurately measured into a 10ml. flask, 1ml. of 0.1% 1-nitroso-2-naphthol solution, 1ml. of 0.05% sodium nitrite solution, and 1ml. of 2.5
N nitric acid are added. The mixture is shaken well and allowed to stand at 50° for 15 minutes. The flask is immersed in an ice bath and the cooled content is brought exactly to 10ml. with ethanol. Absorbancy of the solution is measured at 550mμ. A blank test is carried ont with the same amount of the same reagent, using 1ml. of water in place of the sample solution. Accuracy of this method is σ=1.36% (
n=6).
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Relation between Apparent Dielectric Constant of Compressed Tablet and Contained Water
Isamu Horikoshi, Hajime Sano
1964 Volume 84 Issue 9 Pages
851-856
Published: September 25, 1964
Released on J-STAGE: February 19, 2010
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Solid pharmaceutics were made into tablets by high-pressure, tabletting and apparent dielectric constant and dielectric loss of the tablets were measured. This made it possible to know the difference in the binding of the substrate and water. When water is contained as the water of crystallization, apparent dielectric constant is in the range of 2 to 5, and when present as adsorbed water, as is the case in high molecules, the value was found to become large.
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Temperature Dependence of Dielectric Properties and Pyrolysis of Hydrated Crystals
Isamu Horikoshi, Ikuzo Himuro, Hajime Sano
1964 Volume 84 Issue 9 Pages
856-861
Published: September 25, 1964
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Apparent dielectric constant and dielectric loss of hydrates in accordance with temperature changes were measured and by comparison of these values with weight changes as measured by thermobalance, nature of water in hydrates was examined in detail. This method was found to make simple discrimination of water of crystallization, sorbed water, and free water. The method also enables measurement of melting and decomposition points.
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Influence of Anions for Crystallization
Masayuki Nakagaki, Tadao Fujie
1964 Volume 84 Issue 9 Pages
861-869
Published: September 25, 1964
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Effect of anions on the synthesis of crystalline aluminosilicates was studied in connection with the hitherto reported fact that aluminum chloride can be used instead of sodium aluminate as the aluminum source.
Anions such as C1
-, NO
3-, CO
32-, SO
42-, PO
43-, SCN
-, and I
- were used and their effect was examined by using solutions instead of suspensions, since hydrothermal reaction was effected by the use of sodium aluminate solution as the aluminum source, and silica solution as the silicon source.
When silica/alumina ratio
n is large and alkali is present in excess of above 300%, species P instead of species R was likely to be produced in the presence of anions, especially of PO
43-, in the solution. When
n<1, species Q was formed.
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Reaction of Picolines and their N-Oxides with Methyl Iodide or Benzyl Chloride
Tetsuzo Kato, Yoshinobu Goto, Manabu Hikichi, Takeshi Kawamata
1964 Volume 84 Issue 9 Pages
869-873
Published: September 25, 1964
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α-Picoline 1-oxide undergoes reaction with benzyl chloride in liquid ammonia, in the presence of potassium amide, to form 2-dibenzylmethylpyridine 1-oxide in far larger amounts than phenethylpyridine 1-oxide. This fact indicates that the methyl group had been activated by the presence of N-oxide, compared to the reaction of α-picoline reported by Bergstrom and others.
Reaction of three kinds of picoline and their N-oxides with methyl iodide indicated that the methyl group is activated by the N-oxide group, that β-methyl group has less reactivity, and that the ease of alkylation decreases in the order of γ, α, β in the case of picolines and in the decreasing order of α, γ, β in picoline 1-oxides.
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Syntheses of Wollenberg Type Compounds and Studies on their Structures by Infrared Absorption Spectra
Tetsuzo Kato, Tsunehiro Kitagawa
1964 Volume 84 Issue 9 Pages
874-879
Published: September 25, 1964
Released on J-STAGE: February 19, 2010
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Isoquinoline, lepidine, and methyl isonicotinate react with diketene to form Wollenberg-type compounds (III, IV, and V). These compounds form dehydro derivatives by dehydrogenation. Hydrolysis of the dehydro compound of III affords compounds with the γ-pyrone ring opened. The ultraviolet absorption spectra of these compounds endorsed these reactions. Examination of their infrared absorption spectra indicated that the Wollenberg-type compounds previously reported, including pyridine-diketene adduct (I) and quinoline-diketene adduct (II), take the a-type structure.
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Analysis of Alkylpyridine Derivatives
Bunpei Negishi, Keishiro Nishi
1964 Volume 84 Issue 9 Pages
879-883
Published: September 25, 1964
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Analysis of alkylpyridines in dry distillate of non-fat soybean was examined. Analysis by infrared spectra of the fractional distillate was almost identical with the result of direct analysis of the component by gas chromatography. Twelve alkylpyridines were thus identified.
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Tatsu Kawano, Masako Asakawa
1964 Volume 84 Issue 9 Pages
884-886
Published: September 25, 1964
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Decarboxylase activity of 12 kinds of microorganisms on 21 kinds of amino acid was examined by paper electrophoresis. It was thereby found that
Escherichia coli No.1 effected decarboxylation of arginine, glutamic acid, lysine, ornithine, histidine, aspartic acid, and canavanine,
E. coli K
12 that of arginine, glutamic acid, lysine, ornithine, histidine, tyrosine, aspartic acid, and canavanine,
Streptococcus faecalis ATCC-8043 that of tyrosine,
Proteus vulgaris HX 19 and
Lactobacillus arabinosus 17-5 that of glutamic acid,
Lact. fermenti 36 that of glutamic acid and histidine,
Aerobacter aerogenes No.3059 and
Proteus morganii No.3168 that of glutamic acid and ornithine, and
Clostridium welchii SR 12 that of glutamic and aspartic acids.
Carbon dioxide formed by decarboxylation of glutamic acid by
Lact. arabinosus 17-5 was approximately 90% of the calculated amount in 1 hour so that this cannot be used for the determination of glutamic acid.
Microbiological determination of the decarboxylatlon product of aspartic acid by
E. coli No.1 showed that the amount of α-alanine formed is only about 1% of the calculated and the main decarboxylation product is assumed to be β-alanine.
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The Constituents of the Bark of Firmiana platanifolia SCHOTT et ENDL
Yoshihisa Tanabe, Kiyo Ogura, Shigenori Sakai, Kotaro Takahashi
1964 Volume 84 Issue 9 Pages
887-889
Published: September 25, 1964
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Lupenone, octacosanol, and sucrose were isolated from the bark of
Firmiana platanifolia SCHOTT
et ENDL.
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Synthesis of 5-Nitrofurfural N-Substituted Aminoacylhydrazone Derivatives and Related Compounds
Akio Fujita, Shinsaku Minami, Hideji Takamatsu
1964 Volume 84 Issue 9 Pages
890-893
Published: September 25, 1964
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In order to test their antibacterial activity N-substituted aminoacylhydrazone, N-(substituted phenylsulfonyl)aminoacylhydrazone, and N-(substituted phenyl)carbamoylacetyl-hydrazone derivatives of 5-nitrofurfural (I) and 5-nitro-2-furanacrolein (II) were synthesized.
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Masakazu Aritomi, Kuniko Miyazaki, Tatsuji Mazaki
1964 Volume 84 Issue 9 Pages
894-895
Published: September 25, 1964
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Presence of quercitrin was proved in the leaves of
Rhus javanicus L. (Anacardiaceae), and of rutin and kaempherol 3-L-rhamno-D-glucoside in the leaves of
Melia Azedarach var.
subtripinnata MIQUEL (Meliaceae).
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Masakazu Aritomi, Michiko Shimojo, Tatsuji Mazaki
1964 Volume 84 Issue 9 Pages
895-896
Published: September 25, 1964
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A flavonoid glycoside, C
21H
20O
11⋅3H
2O, m.p. 168-178°, was isolated in a pure state from the flowers of
Gnaphalium affine D. DON (Compositae), and identified as luteolin 4′-β-D-glucoside.
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Syntheses of 1-Substituted 3-Dimethylamino-1, 2, 3, 4-tetrahydroquinoline Derivatives
Isao Satoda, Fuyuki Kusuda, Yoshiharu Matsuo, Nobukiyo Tatewaki
1964 Volume 84 Issue 9 Pages
897-899
Published: September 25, 1964
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As part of attempts to find new antipyretic-analgesic agents, following the previous work on the syntheses of quinoline and cinchophen derivatives, derivatives of 1-acyl-3-dimethylamino-1, 2, 3, 4-tetrahydroquinoline and its related compounds were synthesized. Some examinations were made on their synthetic methods and some of its observations are reported.
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Minoru Tohda, Noriaki Kuwana, Kiyoshi Kawabe
1964 Volume 84 Issue 9 Pages
900-904
Published: September 25, 1964
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Morpholinoacetohydrazide (I) and 4-hydrazinoformylmethyl-4-methylmorpholinium halide (II) were found to have the capacity to separate effectively the two components from a mixture of 4-en-3-one and 1, 4-dien-3-one steroids in a pure state. I and II had the property of selectively binding with 4-en-3-one steroid and their selectivity was equal to that of the Girard reagent. The hydrazone formed with II is water-soluble and separation of the unreacted 1, 4-dien-3-one steroid becomes easy. Actual application of these compounds effected recovery of each component in a high yield from a mixture of these steroids. II is less hygroscopic than the Girard reagent.
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