scholarly journals Microbiological degradation of bile acids, further degradation of a cholic acid metabolite containing the hexahydroindane nucleus by Corynebacterium equi

1977 ◽  
Vol 162 (2) ◽  
pp. 387-397 ◽  
Author(s):  
S Hayakawa ◽  
T Fujiwara
Keyword(s):  
Cholic Acid ◽  
Propionic Acid ◽  
Metabolic Pathways ◽  
Ring Opening ◽  
Initial Step ◽  
Valeric Acid ◽  
Acid Metabolite ◽  
Partial Synthesis ◽  
Initial Oxidation ◽  
Dioic Acid

1. The further degradation of a cholic acid (I) metabolite, (4R)-4-[4alpha-(2-carboxyethyl)-3aalpha-hexahydro-7abeta-methyl-5-oxoindan-1beta-yl]valeric acid (IIa), by Corynebacterium equi was investigated. This organism effected ring-opening and gave (4R)-4-[2alpha-(2-carboxyethyl)-3beta-(3-carboxypropionyl)-2beta-methylcyclopent-1beta-yl]valeric acid (VI). The new metabolite was isolated as its trimethyl ester and identified by partical synthesis. It was not utilized by C. equi. 2. (4R)-4[4alpha-(2-Carboxyethyl)-3aalpha-decahydro-8abeta-methyl5-oxa-6-oxoazulen-1beta-yl]valeric acid (IVa), which is a hypothetical initial oxidation product in the above degradation, was not converted by C. equi into the expected metabolite (VI), but into 3 - [2beta - [(2S) - tetrahydro - 5 - oxofur - 2 - yl] - 1beta - methyl - 5 - oxocyclopent - 1alpha - yl]-propionic acid (VIII), the structure of which was established by partial synthesis. 3. Both the possible precursors of the metabolite (VI), an isomer of the epsilon-lactone (IVa), the gamma-lactone (XIa), and the open form of these lactones, the hydroxytricarboxylic acid (V), were also not utilized by C. equi. 4. Under some incubation conditions, C. equi also converted compound (IIa) and 3-(3aalpha-hexahydro-7abeta-methyl-1,5-dioxoindan-4alpha-yl)propionic acid (IIb) into 5-methyl-4-oxo-octane-1,8-dioic acid (III), (4R)-4-(2,3,4,6,6abeta,7,8,9,9aalpha,9bbeta-decahydro-6abeta-methyl-3-oxo-1H-cyclopenta[f]quinolin-7beta-yl)valeric acid (VII) and probably a monohydroxy derivative of compound (IIa) and compound (III), respectively. 5. The possibility that an initial step in the degradation of compound (IIa) by C. equi is oxygenation of the Baeyer-Villiger type, yielding compound (IVa), is discussed. Metabolic pathways of compound (IIa) to compounds (III), (VI), (VII) and (VIII) are also considered.

scholarly journals Microbiological degradation of bile acids. The preparation of hexahydroindane derivatives as substrates for studying cholic acid degradation

1977 ◽  
Vol 164 (3) ◽  
pp. 709-714 ◽  
Author(s):  
S Hayakawa ◽  
T Takata ◽  
T Fujiwara ◽  
S Hashimoto
Keyword(s):  
Carboxylic Acid ◽  
Cholic Acid ◽  
Propionic Acid ◽  
Good Yield ◽  
Degradation Products ◽  
Chemical Oxidation ◽  
Compound Iiib ◽  
Partial Synthesis ◽  
Arthrobacter Simplex ◽  
Simple Method

Relatively large amounts of 3-(3aalpha-hexahydro-7abeta-methyl-1,5-dioxoindan-4alpha-yl)propionic acid (IIb), which is believed to be one of the intermediates involved in the degradation of cholic acid (I), were needed to identify is further degradation products. A simple method for the preparation of this compound was then investigated. Arthrobacter simplex could degrade-3-oxoandrost-4-ene-17beta-carboxylic acid (IIIa) to 3-(1beta-carboxy-3aalpha-hexahydro-7abeta-methyl-5-oxoindan-4alpha-yl)propionic acid (IVa) in good yield, the structure of which was established by partial synthesis. It was therefore expected that, if a similar degradation by this organism occurred with 17alpha-hydroxy-3-oxoandrost-4-ene-17beta-carboxylic acid (IIIb), which is easily obtained by chemical oxidation of commercially availabe 17alpha-hydroxydeoxycorticosterone, the resulting product, 3-(1beta-carboxy-3aalpha-hexahydro-1alpha-hydroxy-7abeta-methyl-5-oxoindan-4alpha-yl)propionic acid (IVb), could be readily converted chemically into the required dioxocarboxylic acid, (IIb). Exposure of compound (IIIb) to A. simplex produced, as expected, compound (IVb) which was then oxidized with NaBiO3 to give a reasonable yield of compound (IIb).

scholarly journals Microbiological degradation of bile acids. Nitrogenous hexahydroindane derivatives formed from cholic acid by Streptomyces rubescens

1976 ◽  
Vol 160 (3) ◽  
pp. 745-755 ◽  
Author(s):  
S Hayakawa ◽  
S Hashimoto ◽  
T Onaka
Keyword(s):  
Cholic Acid ◽  
Bond Formation ◽  
Valeric Acid ◽  
Amide Bond ◽  
Side Chain ◽  
Mechanism Of Formation ◽  
Partial Synthesis ◽  
Degradative Pathway ◽  
Amide Bond Formation ◽  
New Compounds

The metabolism of cholic acid (I) by Streptomyces rubescens was investigated. This organism effected ring A cleavage, side-chain shortening and amide bond formation and gave the following metabolites: (4R)-4-[4α-(2-carboxyethyl)-3aα-hexahydro-7aβ-methyl-5-oxoindan-1 β-yl]valeric acid (IIa) and its mono-amide (valeramide) (IIb); and 2,3,4,6, 6aβ,7,8,9,9aα,9bβ-decahydro-6aβ-methyl-1H-cyclopenta[f]quinoline-3,7-dione(IIIe)and its homologues with the β-oriented side chains, valeric acid, valeramide, butanone and propionic acid, in the place of the oxo group at C-7, i.e.compounds (IIIa), (IIIb), (IIIc) and (IIId) respectively. All the nitrogenous metabolites were new compounds, and their structures were established by partial synthesis except for the metabolite (IIIc). The mechanism of formation of these metabolites is considered. A degradative pathway of cholic acid (I) into the metabolites is also tentatively proposed.

scholarly journals Microbiological degradation of bile acids. The preparation of some hypothetical metabolites involved in cholic acid degradation

1976 ◽  
Vol 154 (3) ◽  
pp. 577-587 ◽  
Author(s):  
S Hayakawa ◽  
Y Kanematsu ◽  
T Fujiwara ◽  
H Kako
Keyword(s):  
Fatty Acid ◽  
Carboxylic Acid ◽  
Bile Acids ◽  
Cholic Acid ◽  
Valeric Acid ◽  
Side Chain ◽  
Partial Synthesis ◽  
Arthrobacter Simplex ◽  
Acid Degradation ◽  
Oxidation Mechanisms

1. To identify the intermediates involved in the degradation of cholic acid, the further degradation of (4R)-4-[4a-(2-carboxyethyl)-3aa-hexahydro-7ab-methyl-5-oxoindan-1β-yl]valeric acid (IVa) by Arthrobacter simplex was attempted. The organism could not utilize this acid but some hypothetical intermediate metabolities of compound (IVa) were prepared for later use as reference compounds. 2. The nor homologue (IIIa) and the dinor homologue (IIIb) of compound (IVa) were prepared by exposure of 3-oxo-24-nor-5β-cholan-23-oic acid (I) and (20S)-3b-hydroxy-5-pregnene-20-carboxylic acid (II) to A. simplex respectively. These compounds correspond to the respective metabolites produced by the shortening of the valeric acid side chain of compound (IVa) in a manner analogous to the conventional fatty acid a- and b-oxidation mechanisms. Their structures were confirmed by partial synthesis. 3. The following authentic samples of reduction products of the oxodicarboxylic acids (IIIa), (IIIb) and (IVa) were also synthesized as hypothetical metabolities: (4R)-4-[3aa-hexahydro-5a-hydroxy-4a-(3-hydroxypropyl)-7ab-methylindan-1b-yl]valeric acid (Vb) and its nor homologue (VIIa) and dinor homologue (IXa);(4R)-4-[3Aaa-hexahydro-5a-hydroxy-4a-(3-hydroxypropyl)-7ab-methylindan-1b-yl]-pentan-1-ol (Vc); and their respective 5β epimers (Ve), (VIIc), (IXc) and (Vf). 4. In connexion with the non-utilization of compound (IVa) by A. simplex, the possibility that not all the metabolites formed from cholic acid by a certain micro-organism can be utilized by the same organism is considered.

scholarly journals Microbiological degradation of bile acids. Ring a cleavage and 7α,12α-dehydroxylation of cholic acid by Arthrobacter simplex

1969 ◽  
Vol 115 (2) ◽  
pp. 249-256 ◽  
Author(s):  
Shohei Hayakawa ◽  
Yoshiko Kanematsu ◽  
Takashi Fujiwara
Keyword(s):  
Bile Acids ◽  
Cholic Acid ◽  
Valeric Acid ◽  
Hydroxyl Groups ◽  
Partial Synthesis ◽  
Arthrobacter Simplex ◽  
Degradative Pathway ◽  
Acid Degradation

The metabolism of cholic acid by Arthrobacter simplex was investigated. This organism effected both ring a cleavage and elimination of the hydroxyl groups at C-7 and C-12 and gave a new metabolite, (4R)-4-[4α-(2-carboxyethyl)-3aα-hexahydro-7aβ-methyl-5-oxoindan-1β-yl]valeric acid, which was isolated and identified through its partial synthesis. A degradative pathway of cholic acid into this metabolite is tentatively proposed, and the possibility that the proposed pathway could be extended to the cholic acid degradation by other microorganisms besides A. simplex is discussed. The possibility that the observed reactions in vitro could occur during the metabolism of bile acids in vivo is considered.

THE SYNTHESIS OF δ-(3-INDOLYL)-VALERIC ACID AND THE EFFECTS OF SOME INDOL ACIDS ON PLANTS

1936 ◽  
Vol 14b (1) ◽  
pp. 1-5 ◽  
Author(s):  
Richard H. F. Manske ◽  
Leonard Christie Leitch
Keyword(s):  
Propionic Acid ◽  
Valeric Acid ◽  
Methyl Derivative ◽  
Physiological Properties

The synthesis of δ-3 (indolyl) -valeric acid, by a procedure analogous to that employed in the synthesis of its lower homologues, is described. It, as well as a bz-methyl derivative of β-3(indolyl)-propionic acid, which has also been synthesized, was found to possess the plant physiological properties of a phytohormone.

Studies on the production of volatile fatty acids from grass by rumen liquor in an artificial rumen: II. The volatile fatty acid production from dried grass

1957 ◽  
Vol 49 (2) ◽  
pp. 171-179 ◽  
Author(s):  
A. John ◽  
G. Barnett ◽  
R. L. Reid
Keyword(s):  
Fatty Acids ◽  
Acetic Acid ◽  
Propionic Acid ◽  
Metabolic Pathways ◽  
Volatile Fatty Acid ◽  
Volatile Fatty Acids ◽  
Water Soluble ◽  
Fatty Acid Production ◽  
Growing Seasons ◽  
Titration Curves

1. A study has been made of the production of volatile fatty acids obtainable from dried grass and its gross water-soluble and water-insoluble separates, in the artificial rumen, over two growing seasons.2. In contradistinction to fresh grass, the dried grass gives a consistent production of acetic acid proportionately greater than propionic acid, at all stages of maturity, but when aqueous extracts of the dried grass, and the resultant extracted grass, respectively, are examined separately in the artificial rumen, it is found that the former yield preponderating amounts of acetic acid while the latter give amounts of propionic acid equal to, or exceeding, the corresponding productions of acetic acid.3. An examination of the titration curves for the total acids obtained from the dried grass, extracted grass and grass extract runs, indicates an approach to an incomplete relationship between the residual carbohydrate in the extracted grass and cellulose, while the grass extract reveals itself as the chief source of acetic acid in the whole dried grass, the acid being formed very speedily at the start of the run.4. The suggested sources and some of the possible metabolic pathways involved in the formation of v.f.a. from grass are discussed in the text.

Identification of Novel Metabolic Pathways of Pioglitazone in Hepatocytes: N-Glucuronidation of Thiazolidinedione Ring and Sequential Ring-Opening Pathway

2010 ◽  
Vol 38 (6) ◽  
pp. 946-956 ◽  
Author(s):  
Minoru Uchiyama ◽  
Thomas Fischer ◽  
Juergen Mueller ◽  
Minoru Oguchi ◽  
Naotoshi Yamamura ◽  
...  
Keyword(s):  
Metabolic Pathways ◽  
Ring Opening

Studies on double acylation of aromatic hydrocarbons. XI. A total synthesis of 5,6-Dihydro-4H-benz[de]anthracene

1972 ◽  
Vol 25 (7) ◽  
pp. 1521 ◽  
Author(s):  
A Rahman ◽  
BM Vuano ◽  
NM Rodriguez
Keyword(s):  
Total Synthesis ◽  
Propionic Acid ◽  
Intramolecular Cyclization ◽  
Butyric Acid ◽  
Aromatic Hydrocarbons ◽  
Dibasic Acid ◽  
Membered Ring ◽  
Ring Closure ◽  
Partial Synthesis

Starting from ethyl 3-(1-naphthyl)propionate (1), the dibasic acid 4-(4-carboxy-ethyl-I-naphthyl)butyric acid (3) was prepared, which served as a key compound for the synthesis of 5,6-dihydro-4H-benz[de]anthraoene (6) by a double intramolecular cyclization. The monocyolization of the dibasic acid (3) gave rise by a preferential six-membered ring closure, to 3-(1-oxo-1,2,3,4-tetrahydro-9-phenanthryl)propionic acid (7). A partial synthesis of 5,6-dihydro-4H-benz[de]anthracene (6), by succinoylation of perinaphthane followed by usual synthetic steps, is reported as confirmatory evidence of the identity of (6) obtained by double cyclization of the diacid. Some aspects of the orientation of intramolecular acylation are discussed.

scholarly journals Comparative studies of bile salts. A new type of bile salt from Arapaima gigas (Cuvier) (family Osteoglossidae)

1972 ◽  
Vol 126 (5) ◽  
pp. 1161-1170 ◽  
Author(s):  
G. A. D. Haslewood ◽  
L. Tökés
Keyword(s):  
Bile Salt ◽  
Cholic Acid ◽  
Mass Spectroscopy ◽  
Comparative Studies ◽  
Bile Salts ◽  
Trichloroacetic Acid ◽  
Partial Synthesis ◽  
Arapaima Gigas ◽  
New Type

1. Arapaima gigas bile salts were hydrolysed by alkali or cleaved with dioxan–trichloroacetic acid to give cholic acid, arapaimic acid, arapaimol-A and arapaimol-B. 2. I.r., n.m.r. and mass spectroscopy and [α]D measurements indicated that arapaimic acid and arapaimol-A and -B are respectively 2α,3α,7α,12α-tetrahydroxy−5β,25∈-cholestan-26-oic acid, 5β,25R-cholestane-2β,3α,7α,12α,26-pentol and 5β-cholestane-2β,3α,7α,12α,26,27-hexol. 3. Partial synthesis of 2β,3α,7α,12α-tetrahydroxy−5α- and −5β-cholan-24-oic acid and their spectral examination fully confirmed these conclusions. 4. A. gigas bile salts show primitive features in that they comprise alcohol sulphates and a C27 acid; they are also specialized in showing 2β-hydroxylation.

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