2- ethanol 3-Methoxy ethyl acetate

Methoxy-D-Homo-estra-l,3,5(10)-trien-17a-one (96)" (/) Acetic acid (6.4 ml) is added to a stirred solution of estrone methyl ether (93 1.1 g) in ethanol (35 ml) containing potassium cyanide (6 g) at 0°. After being stirred for 1 hr at 0° and 2.5 hr at room temperature, the reactants dissolve and potassium acetate preciptates. Water (65 ml) is added to the reaction mixture and the precipitated solid is collected by filtration. The crude product is dissolved in ethyl acetate and the ethyl acetate solution is washed with water, dried over anhydrous magnesium sulfate and evaporated to dryness under reduced pressure. Recrystallization of a portion of the crude product from cyclohexane-acetone gives 3-methoxy-17a-cyano-estra-l, 3,5(10)-trien-17j5-ol (94a) as needles mp 158.5°. 

Ethanol, 2-methoxy-, 62 Ethanolamines, 62 Ethmylestradiol, 62 Ethion, 62 Ethoprophos, 63 2-Ethoxyethanol, 63 2-Ethoxyethyl acetate, 63 Ethyl acetates, 63 Ethyl acetylene, 63... 

After evaporation of the solvent, a very thick, colorless oil is obtained. This base is dissolved by 200 ml of absolute ethanol and the quantity of HCI to obtain the dihydrochioride is added. It is left for a few hours over ice, dried, washed with approximately 100 ml of anhydrous ether in order to obtain 190 to 195 grams of 1-[2-phenyl-2-methoxy]-ethyl-4-[3-phenyl-3-hydroxy] -propyl-piperazine dihydrochioride after drying at 60°C in vacuo. The yield is 80%. It is recrystallized from absolute ethanol. The product is in the form of white crystalline powder, soluble in water, slightly soluble in alcohol, insoluble in ethyl acetate. 

Ethyl (6-Methoxy-l,2-naphthoquinonyl-6) Cyanoacetate. The above naphthoquinone (21.7 g) is added to a solution of 500 cc of ethanol and 14 cc of ethyl cyanoacetate, followed by the addition of 32 cc triethylamine. A deep purple color will develop and the mixture should be swirled for 4 min to dissolve the quinone completely. A solution of 75.9 g of potassium ferricyanide in 320 cc of water is then added to the solution, causing a thick dark complex to form and separate. Redissolve by adding a soluhon of 24 g of sodium carbonate in 1,600 cc of water. Swirl or stir and filter through diatomaceous filter aid. Acidify the filtrate with 100 cc of 6 M sulfuric acid to precipitate 34.8 g of red-orange powder, which is oven dried at 70°. Reciystallize from ethyl acetate to get 19.3 g, mp 157-158.5°. The remaining filtrate is evaporated to a small bulk and reciystallization from ethyl acetate gives an additional 2.8 g of product. 

The methoxy species was detected by a reaction with acetic acid, ethyl iodide or water (or ethanol) giving methyl acetate, methyl ethyl ether or methanol, respectively. Formates were determined using dimethylsulfate (DMS). 

A solution of the above product (19.2 g, 0.093 mol) in DMF (125 mL) was added to a suspension of sodium hydride (3.08 g, 80% oil dispersion, 0.103 mol) in DMF at 006. When the addition was completed the ice bath was removed and the reaction 20 mixture stirred at ambient temperature for 1 h. The reaction mixture was cooled to 0°C and 2-bromoethyl methylether (13.6 mL, 0.14 mol) was added. The reaction mixture was stirred at ambient temperature for 18 h after which time it was evaporated to dryness. The residue was suspended in brine (100 mL) and extracted with methylene chloride (4x80 mL). The combined extracts were dried (MgS04), filtered and evaporated to a solid which was recrystallized from ethyl acetate to give the desired subject (17.4 g). Chromatography of the mother liquor (silica, 3% ethanol/methylene chloride) furnished more subject which was combined with the first batch to give a total of 19.3 g (78%) of 3,4-dihydro-4-hydroxy-2-(2-methoxy)ethyl-2H-thieno[3,2-e]-l,2-thiazine 1,1-dioxide. 

To a solution of the ethyl 2-(3-methoxy-2,4,5-trifluorobenzoyl)-3-ethoxyacrylate (9.73 g) in ethanol (20 ml) cyclopropylamine (2.0 g) was added dropwise under cooling. After stirring for 2 h at room temperature, the reaction mixture was concentrated and the residue was purified by silica gel column chromatography eluting with n-hexane-ethyl acetate (5 1) to give ethyl 2-(3-methoxy-2,4,5-trifluorobenzoyl)-3-cyclopropylaminoacrylate (7.52 g) as yellowish white crystals, melting point 56°-58°C. 

Recrystallization of 6-nitroBIPS and its simple (methoxy, lower alkyl, halogen) substituted derivatives is often best carried out from pure ethyl acetate (i.e., free of ethanol and acetic acid) with use of decolorizing charcoal. Most dyes have a large temperature coefficient of solubility and crystallize beautifully. 

T etrahy droharmme C13H16N2O (lR)-7-methoxy-l-methyl-2,3,4,9-tetrahydro-1 H-pyrido[3,4-b]indole Slender colorless needles 232-234 °C Blue 225, 269, 296 Chloroform, ethyl acetate, ethanol, methanol... 

Methyl ethyl (7-methoxy-10-methyl-3-phenthiazinyl)malonate is prepared by reacting a solution of sodium (4.37 grams) in anhydrous ethanol (110 cc) with a solution of methyl (7-methoxy-10-methyl-3-phenthiazinyl)acetate (59 grams) in ethyl carbonate (180 cc). 

The reduction of methyl 6-methoxy-2-naphthyl acetate with lithium aluminium hydride in refluxing ether gives 2-(6-methoxy-2-naphthyl)ethanol, which by treatment with PBr3 in refluxing benzene is converted into 2-(6-methoxy-2-naphthyl)ethyl bromide. Further reaction with KCN in refluxing ethanol-water affords 3-(6-methoxy-2-naphthyl) propionitrile, which is finally treated with methylmagnesium iodide in refluxing ethanol. 

The treatment of 2,5-dimethyl-4-azaindole with ethyl magnesium bromide, followed by benzyl chloride, gave 3-benzyl-2,5-dimethyl-4-azaindole. Cyanomethylation of 6-unsubstituted, 6-chloro-, and 6-methoxy-4-methyl-7-azaindole with potassium cyanide and formalin in ethanol at 120° gave the corresponding ethyl 3-acetates in 30, 32, and 3 % yields, respectively. No nitrile-containing product was isolated. 

Acetals and ketals having a second junctional group ate made by these procedures. For example, acrolein reacts with ethyl orthoformate in alcohol solution with ammonium nitrate as catalyst to give acrolein diethyl acetal (73%). On the other hand, it reacts with ethyl ortho silicate with anhydrous hydrogen chloride as catalyst to furnish (i-ethoxypropionaldehyde diethyl acetal (76%). p-Bromoacetophenone and ethyl orthoformate give the corresponding ketal in 65% yield. p-Methoxy- and m-amino-benzaldehyde diethyl acetals are made in a similar way in 96% and 85% yields, respectively. a-Keto esters like ethyl a-keto-n-butytate and ethyl a-keto-tr-valetate are converted to their diethyl ketals in excellent yields by the action of orthoformic ester in ethanol-hydrochloric acid solution. If the reaction is carried out in the presence of ethylene glycol instead of ethanol and, in addition, the volatile products are removed by distillation, then the ethylene ketal is formed in almost quantitative yield (cf. method 133). 

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