In this paper are described the syntheses of all positional and geometrical isomers of n-hexyn-1-ols and n-hexen-l-ols. Each of 2-, 3-, 4- and 5-hexyn-l-ol was synthesized from sodium-acetylide in liquid ammonia in higher yield. Then 2-, 3-, 4-trans- and 5-hexen-l-ol were obtained by the reduction of corresponding n-hexyn-l-ol with sodium in liquid ammonia, and 2-, 3- and 4-cis-hexen-l-ol were prepared by the partial hydrogenation at low temperature using palladium-bariumsulfate catalyst. These alcohols were purified through the 3, 5-dinitrobenzoates. The infrared spectra of above compounds were discussed.

View full abstract

Six new 2-substituted isoflavanones were obtained by catalytic hydrogenation of the corresponding isoflavones. Under the same condition, chromenochromon was reduced to chromanochromanone which was the main skeletal unit of rotenoids. The steric configuration of these compounds is discussed.

View full abstract

By the catalytic hydrogenation of l-dihydrodehydrorotenone, a stereoisomer of dihydrodesoxy-rotenone and two of dihydrorotenone were prepared and termed as dihydrodesoxyallorotenone, dihydroallorotenone-I and -II respectively. Since the catalytic hydrogenation of ethylenic bonds proceeds by cis-addition, it seems reasonable that dihydroallorotenone-I and -II have cis-junction of the rings at C₁₂ and C₁₃, and accordingly l-dihydrorotenone and d-dihydroepirotenone have trans-junction.

View full abstract

Identification of polyalcohols which were produced in large amounts by Saccharomyces rouxii under aerobic fermentation in the concentrated media of sodium chloride and sugar, was carried out by isolating these products in crystalline form from the fermented broth. The products were determined as glycerol and D-arabitol. In the concentrated medium of sodium chloride, about 70% of the polyalcohols produced was glycerol, while in the concentrated sugar medium, the formation of D-arabitol was more markable than glycerol.

View full abstract

From the results of investigation of the polyalcohol productivity of various genera and species of yeasts, the present author has now found that all the yeast strains tested show different individual characteristics in polyalcohol productivities and can be classified in the following six types: (1) solely producing glycerol, (2) solely producing erythritol, (3) producing only D-arabitol, (4) producing erythritol and D-arabitol, (5) producing glycerol and D-arabitol, and (6) producing glycerol, erythritol and D-arabitol.
It was also found that Pichia miso, which was isolated from miso-paste and showed a high osmophilic property, could produce glycerol, erythritol and D-arabitol giving very high yields, 50_??_60%, of sugar consumed. It seems to be worthy of note that this yeast was able to com-pletely dissimilate highly concentrated glucose, such as 30%, producing much polyalcohols as those state above.

View full abstract

(1) With regard to the constituents of the fermentation medium, various nitrogen sources, glucose and their optimum concentrations, as well as the additive influences of various growth substances and metals, were examined.
Solely considering its worth in industrial application, urea seems to be a satisfactory nitrogen source. Its optimum concentration in the medium containing 5% of glucose was found to lie between 0.67 to 0.9%. The growth of cells should be suppressed when the initial con-centration of glucose exceeds 12.5%; therefore a level of 10% gives a better result. Data show-ed that addition of meat and bran extracts gave an increment of about 26% in acid yield.
(2) As for the fermentation condition, after experiments on the incubation temperature, pH and the influence of oxygen supply, etc., reveal that the aerobic condition is favorable for cell growth and accumulation of L-glutamic acid. An oxygen supply around 5 × 10^-6 of K_d is desirable. The optimum incubation temperature was found to lie at 30°C.
A reasonable quantity of L-glutamic acid will be produced if the culture is kept neutral or preferably slightly alkaline by feeding a proper amount of urea aqueous solution throughout in-cubation.
(3) As a conclusion of the above experimental results, the yield of L-glutamic acid reached 45%, on basis of glucose supplied after 30 hours' in-cubation.
(4) By-products such as alanine, α-ketoglutaric acid, pyruvic acid and succinic acid were found at the same time, in the fermentation of L-glu-tamic acid employing Brevibactcrium divaricatum nov. sp.
By observing the time of formation, the kind and the amount of these by-products it was presumed that the L-glutamic acid formation with this strain most probably proceeds from glucose to pyruvic acid, and then to α-ketoglu-taric acid via Krebs TCA Cycle. L-Guutamic acid could be considered to be formed from α-keto-glutaric acid. The reductive amination reaction of α-ketoglutaric acid is assumed to be the main pathway of L-glutamic acid synthesis.

View full abstract

The quinary system KCl-K₂SO₄ MgCl₂- MgSO₄-Mg(OH)₂-H₂O and associated systems KCl-K₂SO₄-Mg(OH)₂-H₂O and MgCl₂-MgSO₄-Mg(OH)₂-H₂O were investigated at 100°. Upon the accomplishment of this quinary system, it was proved that the crystallization field of the new basic triple salt (NS salt B) was so large that various bitterns produced in salt manufacturing factories are included in this field, and it thus became possible to directly separate potassium as sulfate from bittern at 100°

View full abstract

This paper deals with some properties of reversibly inact.^**** TAA effected by means of EDTA. The mechanism of EDTA inactivation was discussed from the view point that EDTA has a conspicious suppressive effect on the reactivation of heat-inact. enzyme, while it has no effect on the active enzyme itself. Particular attention was paid to the problem of calcium transfer along with the progress of inactivation.

View full abstract

(±) Hibalactone, α-piperonylidene-β-piperonyl-butyrolactone, was synthesized by the following method. α-piperonylidene-β-piperonyl-succinic acid dimethylester was reduced with lithium aluminum hydride to 2-piperonylidene-3-piperonyl-1, 4-butanediol, m. p. 117°C. Oxidation of the glycol with manganese dioxide in acetone yielded α-piperonylidene-β-piperonyl-_ϒ-hydroxy-butyraldehyde, which afforded racemic hibalactone, m. p. 154_??_5°, after oxidation with silver oxide and lactonization.

View full abstract

The inducing action of lactic acid on the formation of racemiase was investigated in various aspects. Calcium carbonate revealed remarkable effect on the formation of racemiase, when lactate was not added as an inductor. Characteristic time course of formation of both lactic acid and racemiase in culture of Cl. acetobutylicum was pursued. Pyruvate was capable or promating racemiase activity to some extent in iron-deficient culture. Lactic acid was produced extraordinarily in the presence of cyanide of bicarbonate, but the formation of racemiase was not affected significantly. With intact cellss or Cl. acetobutylicum in adequate conditions, homo-lactic acid fermentation was realized, namely, ninety-seven per cent of glucose consumed was converted to racemic lactic acid. Details of paper chromatographic technique in separating racemic and optically active zinc lactates were presented.

View full abstract

Behaviours of acetone-butanol fermentation bacterium, Clostridium acetobutylicum, towards optically active lactic aci4ls were investigated. As a rule, cells harvested from lactic acid supplemented culture medium surpassed in metabolizing lactic acid as compared with glucosegrown cells. It was pointed out that Cl. acetobutylicum possessed D-lactic dehydrogenase by nature, and that L-lactic acid could be dehydrogenated after its conversion to D-isomer through the action of racemiase. In addition to D-lactic dehydrogenase, it was further indicated that this organism had another type of lactic dehydrogenase or oxidase, which was capable of oxidizing L-isomer with air oxygen in liberating acetic acid and carbon dioxide. Physiological action of racemiase as a mediator between two lactic enzymes, lactic dehydrogenase and. D-lactic acid oxidizing enzyme, was ascertained.
In addition, it is mentioned about pyruvic oxidase and partial inhibition by cyanide to lactic dehydrogenase.

View full abstract

1) E. coli was able to produce α-ketoglutarate when the organism was grown aerobically on the media containing various kinds of carbohydrates; carbohydrates tested were lactose, maltose, sucrose, D-glucose, D-fructose, n-galactose, D-mannose, n-mannitol, L-rhamnose, D-xylose, L-arabinose and glycerin.
2) The effects of the pH of the media upon a-ketoglutarate-fermentation were investigated.
3) A striking effect of inorganic phosphate was observed on the production of α-ketogluta-rate.
4) A statically grown cell of E. coli was found to be capable of inducing a-ketoglutarate-fer-mentation.
5) L lactic acid was potent in the produc-tion of α-ketoglutarate.
6) The action of various reagents was in-vestigated and the inhibiting effects on α-keto-glutarate-fermentation were observed with CuSO₄, AgNO₃, iodoacetate, 2, 4-dinitrophenol, NaN₃, 3-sulfanil-amido-6-methoxy pyridazine and arsenite.
7) A small supply of air into a glucose-medium increased the yield of acetate against decreasing α-ketoglutarate.

View full abstract

Investigations were carried out on the effect of the amount of available oxygen upon the metabolisms of carbonaceous substances in coli-aerogenes bacteria. When E. coli was grown in the presence of glucose, a gentle aeration (a small supply of air) suppressed the accumulation of lactate against increasing the productions of acetate, carbon dioxide and of the bacterial cell. α-Ketoglutarate-fermentation occurred only under a large supply of air. When the cells of coli-aerogenes were incubated under the low levels of oxygen, not only glucose, C₃- (pyruvic, lactic), C₄-dicarboxylic and C₆-tricarboxylic acids but also acetic acid were mainly oxidized to carbon dioxide and water, but little or no formation of a-ketoglutaric acid occurred. The production of α-ketoglutaric acid from various organic acids except C₆-tricarboxylic acids also took place only under the high levels of available oxygen. It was concluded that the direction of oxidative metabolism of substrate-carbon was changeable according to variation of the environmental oxygen level. Relationships among respiration, oxidative fermentation and oxidative assimilation were investigated under various levels of available oxygen.

View full abstract

Further investigations on the oxidation pro-ducts and the oxidative pathway of 5-ketoglu-conic acid by intact and dried cells of Acetobacter suboxydans ATCC 621 gave the following results.
(1) The yield of α-ketoglutaric acid was about 3 0 of 5-ketogluconic acid supplied as the substrate and the former acid produced did not undergo further oxidation.
(2) Besides acetic, succinic, a-ketoglutaric and
glycolic acids as reported in the previous paper, a little amount of pyruvic acid was found in the oxidation products by this organism.
(3) It was ascertained that dried cells of this organism which were capable of oxidizing 5-ketogluconic acid did not oxidize the members of the tricarboxylic acid cycle and related compounds except oxalacetic acid. This result suggests that tricarboxylic acid cycle may not be operative in the degradation processes of 5-ketogluconic acid.
(4) Glycolaldehyde was oxidized by this organism quantitatively but glycolic acid pro-duced could not be oxidized further.
(5) L-Tartaric acid could not be oxidized even though a little amount of glucose was added into the reaction system.

View full abstract

Net synthesis of carotene was demonstrated in disks obtained from carrot roots and grown in test tubes on media containing fructose, glucose or sucrose. Mannitol showed no effect on both growth of the disks and carotene synthesis. Diphenylamine inhibited the synthesis of carotene in the disks in a way somewhat different from that in the case of microorganisms. Although yeast extract stimulated growth of the disks, it showed no effect on carotene synthesis. Addition of possible precursors for carotene synthesis to the medium showed no stimulatory effect except when β-hydroxy-β-methylglutaric acid was added to the medium rich in sucrose.

View full abstract

Oxidation of m-HBA by the eleven bacterial strains which were able to metabolize this compound as a sole source of carbon was carried out. The cultural broths were examined by paperchromatography for detection of intermediates.
Gentisic acid was identified in the culture filtrate of the five strains, while protocatechuic acid by the remaining six strains. Protocatechuic acid was not detected in all the cultural broth of bacteria which belong to the gentisic acid path type, and vice versa.
Strains which possess the gentisic acid path were Pseudomonas ovalis (two strains), Micrococcus ureae, and an unidentified Bacterium and a strain of Aerobacter. Strains which have the proto-catechuic acid path were Pseudomonas dacunhae (five strains) and Pseudomonas cruciviae.
An unknown keto acid was detected as its 2, 4-dinitrophenylhydrazone from the incubation mixture of the resting cell of Pseudomonas ovalis S-5 and gentisic acid. This new keto acid was most probably the direct intermediate after the cleavage of gentisic acid.
Acknowledgement The authors wish to express their sincere thanks to Prof. Emeritus K. Sakaguchi for his continous guidance throughout this work.

View full abstract