Absolute ethanol, hydrolyzing

The crude ketal from the Birch reduction is dissolved in a mixture of 700 ml ethyl acetate, 1260 ml absolute ethanol and 31.5 ml water. To this solution is added 198 ml of 0.01 Mp-toluenesulfonic acid in absolute ethanol. (Methanol cannot be substituted for the ethanol nor can denatured ethanol containing methanol be used. In the presence of methanol, the diethyl ketal forms the mixed methyl ethyl ketal at C-17 and this mixed ketal hydrolyzes at a much slower rate than does the diethyl ketal.) The mixture is stirred at room temperature under nitrogen for 10 min and 56 ml of 10% potassium bicarbonate solution is added to neutralize the toluenesulfonic acid. The organic solvents are removed in a rotary vacuum evaporator and water is added as the organic solvents distill. When all of the organic solvents have been distilled, the granular precipitate of 1,4-dihydroestrone 3- methyl ether is collected on a filter and washed well with cold water. The solid is sucked dry and is dissolved in 800 ml of methyl ethyl ketone. To this solution is added 1600 ml of 1 1 methanol-water mixture and the resulting mixture is cooled in an ice bath for 1 hr. The solid is collected, rinsed with cold methanol-water (1 1), air-dried, and finally dried in a vacuum oven at 60° yield, 71.5 g (81 % based on estrone methyl ether actually carried into the Birch reduction as the ketal) mp 139-141°, reported mp 141-141.5°. The material has an enol ether assay of 99%, a residual aromatics content of 0.6% and a 19-norandrost-5(10)-ene-3,17-dione content of 0.5% (from hydrolysis of the 3-enol ether). It contains less than 0.1 % of 17-ol and only a trace of ketal formed by addition of ethanol to the 3-enol ether. 

When the reaction is run with potassium fert-butoxide in THF at -5°C, one obtains (after hydrolysis) the normal Knoevenagel product (32), except that the isocyano group has been hydrated (16-65). With the same base but with DME as solvent the product is the nitrile (33). When the ketone is treated with 31 and thallium(I) ethoxide in a 4 1 mixture of absolute ethanol and DME at room temperature, the product is a 4-ethoxy-2-oxazoline (34). Since 33 can be hydrolyzed to a carboxylic acid and 34 to an a-hydroxy aldehyde, this versatile reaction provides a means for achieving the conversion of RCOR to RCHR COOH, RCHR CN, or RCR (OH)CHO. The conversions to RCHR COOH and to RCHR CN have also been carried out with certain aldehydes (R = H). 

Both sulfonyl chloride and isothiocyanate will hydrolyze in aqueous conditions therefore, the solutions should be made freshly for each labeling reaction. Absolute ethanol or dimethyl formamide (best grade available, stored in the presence of molecular sieve to remove water) should be used to dissolve the reagent. The hydrolysis reaction is more pronounced in dilute protein solution and can be minimized by using a more concentrated protein solution. Caution DMSO should not be used with sulfonyl chlorides, because it reacts with them. 

Formyl-2,3,5,6,7,8-hexahydro-l//-telluroxantliene1 34.6 g (0.1 mol) of bis[2-formyl-l-eyelohexen-l-yl] tellurium are dissolved in the minimum amount of absolute ethanol, a solution of 0.1 mol of sodium methoxide in methanol is rapidly added, and the mixture is stirred for 10 min. The resultant reaction mixture is then hydrolyzed with water, the hydrolyzed mixture is extracted with diethyl ether, and the solvent is evaporated from the extract. The resultant oil is extracted with hot petroleum ether and the extract is cooled to precipitate a red solid yield 11.5 g (35%) m.p. 86°. 

Ethyl cyanoacetate condenses with ketones and ammonia in absolute ethanol at 0-5° to give 44-73% yields of cyclic dicyanoimides. Endocyclic ketones may be used, giving imides in which the two radicals are p>art of an alicyclic ring. The imides are hydrolyzed and decarboxylated in almost theoretical yields to yS,/S-disubstituted glutaric acids. A similar reaction takes place between aldehydes or ketones and cyanoacetamide, NCCHjCONHj, in the presence of piperidine or potassium hydroxide. When aldehydes are used, the condensation products are dicyanoamides, RCH[CH(CN)CONHj]j, rather than cyclic imides. 

REDUCTIVE DIMERIZATION AND ISOMERIZATION OF METHYLPHENYL-ACETYLENE. In a manner similar to the foregoing method, 5.8 g (50 mmol) of the methylphenylacetylene and 35 mL of ethyl ether were vigorously stirred with 350 mg (50 mg-at) of lithium pieces at 20 °C for 4 h. The excess lithium was removed, and the red solution was hydrolyzed. Removal of the volatiles in vacuo and crystallization of the residue from absolute ethanol gave 2.2 g (38%) of colorless leaflets of (E,E)-2,3-dimethyl-l,4-diphenyl-l,3-butadiene (mp 132-133 °C) (16). When the reaction was carried out on the same scale but in 30 mL of THF at -10 °C for 24 h, hydrolytic work-up (the addition of water followed by extraction with ether) gave an organic layer containing (E, E)-2,3-dimethyl-1,4-diphenyl-1,3-butadiene and isomers of methylphenylacetylene. 

Chloroacridine (recrystallized from absolute ethanol) (1.08 g, 5.1 mmoles) and NaN (350 mg, 5.4 mmoles) are dissolved in methanol and warmed to 60° for 20 min. NaCl forms after a few minutes. The methanol is evaporated, and 50 ml of water are added to dissolve NaCl and to hydrolyze the remaining 9-chloroacridine to acridone. Recrystallization is from MeOH-H-O (0.85 g, 77%). The compound has been prepared by refluxing 9-chloroacridine and sodium azide in aqueous acetone and also by oxidizing the hydrazo compound with HNO- in 2 N HCl. ... 

HPLC has been used to determine the levels of genistein, daidzein, biochanin A, formononetin, and equol in foods, formulas, and drinks consumed in Australia. Samples are diluted with water (1 10, v/v), hydrolyzed enzymatically (glucosidase 0.4 x/mL, 24 h at 37°C), and the aglycone form extracted in absolute ethanol, filtered and injected onto the HPLC. The lower limits of detection with this procedure for daidzein, genistein, and equol are 54, 48, and 94 ng/mL, respectively, within batch precision of 0.7%-3.0% CV (Knight et al., 1998). 

Zirconium propoxide (Aldrich, 26.6 g) was mixed with absolute ethanol (Merck, 336.6 g) and stirred for 10 min to obtain a homogeneous solution under N2 at room temperature, then 0.47 cm of 0.28 M HCl aqueous solution was dropped slowly into the above mixture to catalyze the sol-gel reaction for 3 h. After that, an appropriate amoimt of urea-alcohol-water (1 5 1 weight ratio) solution was added to the hydrolyzed solution tmder vigorous stirring to act as template. The amount of added solution was fixed in order to obtain a template concentration of 10% by weight in the final material. The gel was kept in a beaker at room temperature till solidification. The solid was grounded into powder and extracted by distilled water for three periods of 24 h, in a system with continuous stirring to remove urea. Finally, it was calcined at 100, 200, 300, and 400°C for 24 h (Zrjx samples, where X is the calcination temperature). 

Readily soluble in water the dihydrate crystallizes from concentrated solution at greater dilutions, hydrolyzes with formation of Sn(OH)Cl quite soluble in acetone, amyl alcohol, ethyl acetate, and absolute methanol and ethanol. 

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