Methyl 7-deoxycholate

For the addition to C6o of two o-quinodimethane groups linked by tethers including methyl deoxycholate, hyodeoxycholate, and chenodeoxycholate units, we refer to Section IV.A.l.c.151... 

Miki, K. Masui, A. Kasai, N. Miyata. M. Goonew ar-dena, W. Shibakami, M. Takemoto, K. Structure of a 2 1 addition compound of methyl deoxycholate with methanol. Acta Crystallogr., C 1989. 45, 79. 

Partial separations of the substituted methyl allocholanoates have now been achieved by crystallization. Kallner (41, 45) has reported the removal of 82% of the radioactivity after three crystallizations of a mixture of methyl allolithocholate- H and methyl lithocholate 90% of the tritium was removed by several crystallizations of a mixture of methyl lithocholate- H and allolithocholate. Similarly, more than 90% of the radioactivity was removed from a mixture of methyl deoxycholate- H and allodeoxycholate after three crystallizations from aqueous acetic acid or aqueous methanol. Methyl 3/3,12a-dihydroxy-5 -cholanate was separated from methyl deoxy-cholate by crystallization from aqueous methanol. Thomas et al. (46) reported the separation of 3a,6/3-dihydroxy-5 - or 3a,6a-dihydroxy-5 -cholanoic acid from 3a,6/3-dihydroxy-5 -cholanoic acid by crystallization from aqueous acetone or a mixture of methanol, ether, and hexane. 

Relative retention times for the columns labeled OH refer to methyl deoxycholate = 1.00 for the columns labeled TMS (trimethylsilyl ethers) refer to the bis (TMS) ether of methyl deoxycholate = 1.00. Absolute times of elution of methyl deoxycholate were 3% QF-1, 29.0 min 3% OV-1, 38.4 min 3% OV-17, 44.0 min methyl deoxycholate was injected simultaneously with each ester. Absolute times of elution of the bis (TMS) ether of methyl deoxycholate were 3% QF-1, 10.0 m in 3% OV-1, 27.3 min 3% OV-17, 14.2 min this derivative was injected simultaneously with each ether (60). 

The relative retention times of the trimethylsilyl (TMS) ethers in Table III are related to the TMS ether of methyl deoxycholate as 1.00. The TMS ethers were prepared from a mixture of trimethylsilyl chloride, hexamethyl-disilazane, and dry pyridine according to Makita and Wells (61) to assure the formation of the complete derivative (cf. Chapter 5 for a discussion of the preparation of partial TMS derivatives). These TMS ethers are generally eluted more rapidly from the column than the free alcohols the TMS ethers of the equatorial 3 3-ols of the allocholanates are generally retained on the column longer than the corresponding 3/3 ethers of the 5/3-epimers (60). On the other hand, the TMS ethers of the allo-3a-ol, 3a,7a-diol, 3a,7a,12a- and 3a,6/3,7/3-triols are eluted from each of the three phases before their respective 5/3-cholanates. However, the TMS ether of methyl allodeoxycholate is eluted before the TMS ether of methyl deoxycholate on QF-1, but not on OV-1 or OV-17 (60). Hoshita et al. (39) observed that the TMS ethers of... 

Retention times of a few of the trifluoracetates (TEA) of allocholanates have been reported, all relative to methyl deoxycholate. Eneroth and Sjovall (62) reported values of 1.18 and 1.09 for TEA esters of methyl 3j3,6a-dihy-droxy-5a-cholanoate and 3, 6j8-dihydroxy-5a-cholanoate, respectively, on 0.5%QE-1, and 1.37 for the TEA ester of methyl allocholate on 3 %QE-1 at 230°C. Tsuda et al. (63) reported relative retention times of 1.55 and 1.39 for the TEA esters of methyl 3/3,6a-dihydroxy-5a-cholanoate and 3, 6 -dihydroxy-5a-cholanoate, respectively, on 0.5-2.3% SE-30 at 220°C. 

During studies on the metabolism of deoxycholic acid in the rabbit (34) a new acid was isolated from rabbit feces, whose methyl ester was eluted from alumina slightly before methyl deoxycholate, showed a mass spec-... 

Relative to methyl deoxycholate unless otherwise indicated. 

Retention times given relative to the bis(trimethylsilyl) ether of methyl deoxycholate. 

The quantification of methyl cholanoates requires the resolving power of a QF-1 column for complex mixtures. Only little tailing with di- and trihydroxy bile acid methyl esters should be permitted. Under acceptable conditions the response relative to methyl deoxycholate is of the order 0.90-1.25 for mono- and disubstituted methyl cholanoates but may be as low as 0.50 for the trisubstituted compounds (18). Poor responses are probably due to column imperfections and not so much caused by the detection unit in the linear range. 

With a purified enzyme preparation from Clostridium perfringens, Roovers et al. (36) cleave conjugated bile acids directly in plasma. Proteins are then precipitated with Ba(OH)2-saturated ethanol (123) and the supernatant is taken to near dryness. The residue is dissolved in a toluene-isopropanol-methanol-30 % aqueous NaOH (10 20 20 6, v/v) mixture, water is added, and neutral lipids removed by light petroleum extraction. Bile acids are then obtained by acidification and diethyl ether extraction. The bile acids are then methylated and analyzed as above except that the bile acid methyl esters are acetylated before chromatography on 1 % XE-60 columns at 250°C. With this column the following retention times relative to that of the diacetoxy derivative of methyl deoxycholate were found for the following acetate methyl ester derivatives lithocholic, 0.60 23-nor-deoxycholic acid (internal standard), 0.77 chenodeoxycholic acid, 1.24 and cholic acid, 1.88. The deoxycholic acid derivative was eluted after 9.0 min and methyl 5 3-cholanoate after 0.32 min. 

Methyl oleate Methyl oleate Methyl lithocholate Methyl lithocholate Methyl lithocholate Methyl lithocholate Methyl deoxycholate Methyl deoxycholate Methyl deoxycholate Lithocholic acid Anasil B Silica gel G Silica gel G Silica gel G Silica gel G Anasil B Silica gel G AnasU B Silica gel G Silica gel G... 

The monoacid pentaester 6 is a versatile intermediate, nearly perfect for the synthesis of a series of compounds like tiiose above described. However, its synthesis (14) largely accounts for the low yield observed in the preparation of Ic. Furthermore, the conversion of methyl deoxycholate into the corresponding 3/ -NH2 derivative 14 (see Figure 5 Research route) involves the intermediate production of the SjS-Ns derivative 15. Although the latter proved a perfectly safe compound, we must underline that i) the reagent (Le. diphenylphosphoryl azide) which is used in the Mitsunobu reaction is extremely expensive ii) alternative approaches to generate the azide by phase tiansfer catalysed... 

Derivatives Acetylated methyl esters are the most suitable derivatives (e.g., deoxycholic acid and cholic acid). 

Cherry and Crandall in 1932 (86) used olive oil as substrate with gum acacia as the emufsTfier. This method has served as the basis for a number of modifications that increased the stability of the emulsion, decreased incubation time and gave better precision. When a serum sample is incubated with a stabilized olive oil emulsion, lipase acts at the interface of substrate and water to hydrolyze olive oil into fatty acid plus diglycerides, and to a small extent to monoglycerides and glycerol. The bile salt sodium deoxycholate activates the reaction. These methods measure the liberated fatty acids by titration with a standardized NaOH solution. An indicator such as phenolphatalein, thymolphthalein or methyl red or a pH meter are used to detect the end point. 

Selective hydrolysis of the 3a-acetoxy-group of fully acetylated cholic acid derivatives has been achieved with methanolic HCl. The hydrolysis occurs more rapidly than the methylation of the side-chain carboxylic acid. The 3-monosulphates of cholic, chenodeoxycholic, and deoxycholic acids have been prepared using this selective hydrolysis on the fully acetylated methyl esters. The resultant 3a-hydroxy-compounds were then treated with chlorosulphonic acid and the... 

Fig. 5.4.4a Methyl ester-trimethylsilyl (TMS) ethers of BAs from a plasma sample, b n-Butyl ester-TMS ethers of BAs from a plasma sample (adapted from [15]). 1 Nor-cholic acid, 2 litho-cholic acid, 3 deoxycholic acid, 4 chenodeoxycholic acid, 5 cholic acid, 6 ursodeoxycholic acid, a cholesterol, b sitosterol)...

The bile acids are produced in the liver by the metabolism of cholesterol. They are di- and trihydroxylated steroids with 24 C atoms. The structure of cholic acid was seen earlier (Sec. 6.6). Deoxycholic acid and chenodeoxycholic acid are two other bile acids. In the bile acids, all the hydroxyl groups have an a orientation, while the two methyl groups are /3. Thus, one side of the molecule is more polar than the other. However, the molecules are not planar but bent because of the cis conformation of the A and B rings. 

A mixture of lentil lectin-reactive glycoproteins from pig lymphocyte-plasma membrane was isolated by lentil lectin-Sepharose chromatography of sodium deoxycholate-solubilized membranes.445 Eighty-seven percent of the protein applied (17% of hexose) passed through unretarded, and 13% of the applied protein (83% of hexose) was bound, and eluted with methyl a-D-glucopyranoside solution. Recovery was 95% of the material applied, in contrast to the recovery in similar experiments conducted on con A-Sepharose columns (80% recovery).850 The eluate from the lentil column, which contained at least ten glycoproteins, blocked lymphocyte transformation induced by lentil or kidney-bean lectins.445... 

The anaesthetic steroid 3a-hydroxy-5a-pregnane-ll,20-dione has normal conformational features, both in the crystal and in solution. X-Ray data show that deoxycholic acid can form an inclusion complex in which alternate molecules of dimethyl sulphoxide and water are held in canals formed by helically arranged host molecules.Six different crystalline forms of 17a-ethynyloestradiol have been recognized. X-Ray structural data are reported for 3-methoxy-2-aza-oestra-l,3,5(10)-trien-17/3-yl acetate, 3/3-hydroxypregn-5-en-20-one (pregnenolone), 5a-cholest-2-ene, 3/3-bromo- and 3/3-chloro-cholest-5-enes, and cholesteryl acetate (at 123 K), benzoate, chloroformate, ° laurate, methyl carbonate, and 24-norcholesteryl acetate. ... 

Deoxycholic acid Dicyclohexyl carbodiimide Diethyl amine Disofenin Docusate sodium Edamine Exametazime Gluceptate sodium Gluceptate calcium Glucuronic acid Guanidine HCl lofetamine HCl Lactobionic acid Lidofenin Medrofenin Medronate disodium Medronic acid Methyl boronic acid Methyl cellulose Methylene blue... 

An examination of the behaviour in the solid state of guest molecules such as aliphatic ketones ( acetone and ethyl methyl ketone) and suromatic ketones (acetophenone and /7>Cl-acetophenone) in deoxycholic and apocholic acids has identified stereospecific addition of the guest molecules to the host by a hydrogen abstraction radical combination path. A flash photolytic study of fluorenone has shown that the triplet state reacts with electron rich alkenes in an electron transfer process. 

Deoxycholic Acid, (3ct,5t3,I2a) 3,I2-Dihydroxy-5 cholan-2d <>ic acid- l70-(i-methyl-3-carboxypropyl)etio-cbolane-3a, 12 -diol desoxycholic acid, mol wt... 

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