Estrone sulfuric acid

The sulfate group can be transferred easily, i.e. in exergonic reactions, to phenols and alcohols. These sulfuric esters have long been known as detoxication and excretion forms of various foreign substances and metabolic products. They include phenol sulfuric acid, indoxyl sulfuric acid (indican), and estrone sulfuric acid. The sulfuric esters of carbohydrates arise presumably in a similar manner (Chapt. XVII-7). 

Estrone methyl ether (100 g, 0.35 mole) is mixed with 100 ml of absolute ethanol, 100 ml of benzene and 200 ml of triethyl orthoformate. Concentrated sulfuric acid (1.55 ml) is added and the mixture is stirred at room temperature for 2 hr. The mixture is then made alkaline by the addition of excess tetra-methylguanidine (ca. 4 ml) and the organic solvents are removed. The residue is dissolved in heptane and the solution is filtered through Celite to prevent emulsions in the following extraction. The solution is then washed threetimes with 500 ml of 10 % sodium hydroxide solution in methanol to remove excess triethyl orthoformate, which would interfere with the Birch reduction solvent system. The heptane solution is dried over sodium sulfate and the solvent is removed. The residue is satisfactory for the Birch reduction step. Infrared analysis shows that the material contains 1.3-1.5% of estrone methyl ether. The pure ketal may be obtained by crystallization from anhydrous ethanol, mp 99-100°. Acidification of the methanolic sodium hydroxide washes affords 10-12 g of recovered estrone methyl ether. 

Acetylene and Potassium in Liquid Ammonia Potassium (40 g) is dissolved in 1 liter of dry liquid ammonia. Dry acetylene is then bubbled into the solution until the blue color is discharged. A solution of 15 g of estrone in 300 ml of dioxane is prepared and diluted with 300 ml of ether, cooled, and added to the potassium acetylide solution over a period of 10 min. The liquid ammonia is allowed to evaporate, an additional 500 ml of ether is added, and the mixture is allowed to stand overnight. About 3 liters of 5 % sulfuric acid is added and the organic layer separated. The water layer is re-extracted with fresh ether, and the combined ether extracts are washed twice with 5 % sodium carbonate solution, th6n several times with water, and finally evaporated under reduced pressure. The residue is dissolved in 150 ml of methanol, then an equal quantity of hot water is added and the mixture cooled. The precipitated solid is collected, washed with cold 60 % methanol and crystallized once from methanol-water to give 14.8 g (85%) of 17a-ethynylestradiol mp 143-144°. 

In about 250 cc of liquid ammonia (cooled with dry ice and acetone) are dissolved about 7.5 g of potassium and into the solution acetylene is passed until the blue color has disappeared (about 3 hours). Then slowly a solution or suspension of 3 g of estrone in 150 cc of benzene and 50 cc of ether is added. The freezing mixture is removed, the whole allowed to stand for about 2 hours and the solution further stirred overnight. Thereupon the reaction solution is treated with ice and water, acidified with sulfuric acid to an acid reaction to Congo red and the solution extracted five times with ether. The combined ether extracts are washed twice with water, once with 5% sodium carbonate solution and again with water until the washing water is neutral. Then the ether is evaporated, the residue dissolved in a little methanol and diluted with water. The separated product is recrystallized from aqueous methanol. The yield amounts to 2.77 g. The 17-ethiny I-estradiol-3,17 thus obtained melts at 142°C to 144°C . 

The estrogens biosynthesized in the placental compartment are transferred to both the mother and the fetus mostly in an uriconjugated form. Nonetheless, part of the estrone which reache.s the fetal compartment is conjugated with sulfuric acid, while some of the estrone w hich reaches the maternal compartment is also conjugated with sulfuric acid, and a small quantity with glucuronic acid (Purdy el al., 1961). 

Commercial facilities constructed include a coal gasification plant for synthesis gas manufacture, raw gas cleanup and separation facilities, a sulfur recovery unit, a coal-fired steam plant, and chemical plants to produce methanol, methyl acetate, acetic acid, and acetic anhydride. In the 1980s, these plants gasified approximately 900 tons of coal/day to produce annually over 500 million lb of acetic anhydride, 150 million lb of acetic acid, 390 million lb of methyl acetate, 365 million lb of methanol, and 15 million lb of sulfur. An expansion in 1991 more than doubled the capacity for methyl acetate, acetic acid, and acetic anhydride. Approximately one billion lb of acetic anhydride, one of Eastman s key raw materials, is used each year in making photographic film base, Tenite cellulosic plastics, Estron acetate for filter tow, textile yarns, and coatings chemicals. 

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