Methyl desoxycholate

Metiiylcoumarin, 24, 69 Methylcyclohexane, 21, 16 Methyl desoxycholate, 24, 41 Methyl a,/3-dibromopropionate, 20, 82 N-Methyl-3,4-dihydroxyphenyl-... 

A. Methyl desoxycholate. To a cooled solution of 100 g. (0.255 mole) of desoxycholic acid (Note 1) in 11. of methanol is added carefully 50 ml. of acetyl chloride. The solution is allowed to stand overnight at room temperature (Note 2) and is then diluted with cold water until just turbid. Crystallization is induced by scratching and seeding, if necessary. When much of the ester has crystallized, the mixture is further diluted to about 2.5 1. and allowed to stand for 30 minutes until crystallization is complete. The ester is collected on a filter, washed with water, and dried. The yield is 100-103 g. (97-100%) of material which melts at 95-100° (Note 3). 

This methyl desoxycholate is pure enough for most purposes, but if desired it may be recrystallized from methanol or from a mixture of ether and petroleum ether. 

The solution of methyl desoxycholate in dry benzene is conveniently prepared by dissolving the ester in 900 ml. of ordinary benzene and distilling the excess solvent. 

Dehydrogenation of 3-kelo steroids. The dehydrogenation of 3-keto steroids to l,4-diene-3-ones with benzeneseleninic anhydride (8, 31) can be carried out in comparable yield by use of a process in which the benzeneseleninic anhydride is used in catalytic amounts and is continuously regenerated from diphenyl diselenide by oxidation with iodylbenzene. In practice, m-iodylbenzoic acid is a more convenient reagent, since m-iodobenzoic acid is easily recovered. 12-Keto and 12-hydroxy steroids arc oxidized by the catalytic system to A9(1 - -keto steroids in high yield. In fact, methyl desoxycholate (1) can be oxidized in this way directly to the trienedione 2 in 64% yield.1... 

One of the simplest and most efiicient processes for accomplishing the shift of the C-12 oxygen function to C-11 is due to Gallagher. Methyl desoxycholate (Fig. 1) upon partial acetylation at C-3 and oxidation at C-12 leads readily to methyl 3a-acetoxy-12-ketocholanate (I). Bromination... 

Methylation of hydrocortisone/prednisolone in positions C-4, C-7, C-12, and C-21 failed to give useful products. Methylation at C-16, in contrast, led to 16a- and 16p-methyl-9a-fluoroprednisolones which were exceptionally useful. Both series were prepared using 3a-acetoxy-5a-pregn-16-ene-ll,20-dione derived from desoxycholic acid (80). A much shorter route was subsequently developed from... 

Esterification—Continued by azeotropic distillation with benzene, 22, 38 by nitric acid, 22, 65 of desoxycholic acid, 24, 41 of lactic acid, 26, 4 of linoleic acid, 22, 77 of linolenic acid, 22, 83 of pyruvic acid with use of methyl ester column, 24, 72 Ester interchange, 26, 5, 19 between polylactic acid and allyl alcohol, 26, 5... 

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... 

Methylcarboxylamine. See Methyl isocyanate L7-P-(1-Methyl-3-carboxypropyl) etiocholane-3a,12o-diol. See Desoxycholic acid Methylcatechol o-Methylcatechol. See Guaiacol... 

Pyridoxol hydrochloride. See Pyridoxine HCI Pyridylcarbinol 3-Pyridylcarbinol 3-Pyridylmethanol. See Pyridine-3-methanol Pyroacetic acid Pyroacetic ether. See Acetone Pyrobenzol Pyrobenzole. See Benzene Pyrocellulose. See Cellulose Pyrochol. See Desoxycholic acid Pyrodextrin. See Dextrin 2-Pyrol. See 2-Pyrrolidone Pyroligneus acid. See Acetic acid Pyromucic aldehyde. See Furfural Pyrophyllite. See Aluminum silicate Pyrosulfurous acid disodium salt. See Sodium metabisulfite Pyroxylic spirit. See Methyl alcohol m-Pyrrole. See N-Methyl-2-pyrrolidone 2-Pyrrolidinone a-Pyrrolidinone. See 2-Pyrrolidone 2-Pyrrolidinone, 1-dodecyl-. See Lauryl pyrrolidone 2-Pyrrolidinone, 1-ethenyl, hexadecyl homopolymer CAS 63231-81-2... 

---