Abietic acid, dehydro


Gently warm a mixture of 32 g. (32 ml.) of ethyl acetoacetate and 10 g. of aldehyde-ammonia in a 400 ml. beaker by direct heating on a gauze, stirring the mixture carefully with a thermometer. As soon as the reaction starts, remove the heating, and replace it when the reaction slackens, but do not allow the temperature of the mixture to exceed 100-no the reaction is rapidly completed. Add to the mixture about twice its volume of 2A -hydrochloric acid, and stir the mass until the deposit either becomes solid or forms a thick paste, according to the quality of the aldehyde-ammonia employed. Decant the aqueous acid layer, repeat the extraction of the deposit with more acid, and again decant the acid, or filter off the deposit if it is solid. Transfer the deposit to a conical flask and recrystallise it twice from ethanol (or methylated spirit) diluted with an equal volume of water. The i,4-dihydro-collidine-3,5-dicarboxylic diethyl ester (I) is obtained as colourless crystals, m.p. 130-131°. Yield 12 5 g,  [c.296]

Gently warm a mixture of 32 g. (32 ml.) of ethyl acetoacetate and 10 g. of aldehyde-ammonia in a 400 ml. beaker by direct heating on a gauze, stirring the mixture carefully with a thermometer. As soon as the reaction starts, remove the heating, and replace it when the reaction slackens, but do not allow the temperature of the mixture to exceed 100-110° the reaction is rapidly completed. Add to the mixture about twice its volume of 2A -hydrochloric acid, and stir the mass until the deposit either becomes solid or forms a thick paste, according to the quality of the aldehyde-ammonia employed. Decant the aqueous acid layer, repeat the extraction of the deposit with more acid, and again decant the acid, or filter off the deposit if it is solid. Transfer the deposit to a conical flask and recrystallise it twice from ethanol (or methylated spirit) diluted with an equal volume of water. The i,4-dihydro-collidine-3,5-dicarboxylic diethyl ester (I) is obtained as colourless crystals, m.p. 130 -131°. Yield 12-5 g-  [c.296]

Residual aromatic ether concentrations are determined from the absorbance at 278 mfi of the crude reduction products in methanol solution. Steroidal ether concentrations of 1 mg/ml are employed. The content of 1,4-dihydro compound is determined, when possible, by hydrolysis to the a, -unsaturated ketone followed by ultraviolet analysis. A solution of the crude reaction product (usually 0.01 mg/ml cone) in methanol containing about 1/15 its volume of water and concentrated hydrochloric acid respectively is kept at room temperature for 2 to 4 hr. The absorbance at ca. 240 mfi is measured and, from this, the content of 1,4-dihydro compound can be calculated. Longer hydrolysis times do not increase the absorbance at 240 mp..  [c.50]

Q Preparation of 2-Acetyi-3-Methyi-5-(2-Oxo-2,5-Dihydro-4-Furyi)Benzo[b]Furan (3556 CB) (1) A suspension of 2 grams of the compound prepared according to (B) in 20 ml of concentrated hydrochloric acid, is heated to about 50°C, just until it dissolves. Thereafter it is heated for 2 minutes to 70°C, just until precipitation commences. The mixture is allowed to cool, diluted with water, filtered, the residue washed, dried, and sublimed at 200°C and 0.1 mm pressure, 1.4 grams of product (Yield 70%) Is obtained, MPc = 218°-221°C. A second sublimation produces a chemically pure product, MP = 221°-222°C.  [c.142]

Naphtho[2,l-e][l,2,4]triazine-l-carboxylic acid, 3-0X0-1,4-dihydro-synthesis, 3, 453 Naphthotriazines betaines synthesis, 2, 69 N aphtho-1,2,4-triazines synthesis, 3, 445 Naphtho[ 1,2- e][ 1,2,4]triazines synthesis, 3, 433 Naphthop, 1 -e][l, 2,4]triazines synthesis, 3, 433  [c.706]

The isotopic purity of the product is usually about 48-62%, the rest of the material being mainly undeuterated. (An alternate preparation of a-mono-deuterio ketones of high configurational and isotopic purity is the mild oxidation of cis- or tra 5-deuterated alcohols under Jones conditions, see sections V-D and VII-A.) Treatment with zinc in acetic acid-OD has also been applied to the deiodination of 2a-iodoandrost-4-ene-3,17-dione. In a slightly modified version the iodine in 19-iodocholesterol acetate has been replaced with tritium by using tritium oxide as the isotope source/  [c.202]

One gram of 6,7-dihydro-5H-dibenz[c,e] azepine hydrochloride was dissolved in water, made alkaline with concentrated ammonia, and the resultant base extracted twice with benzene. The benzene layers were combined, dried with anhydrous potassium carbonate, and mixed with 0.261 g of allyl bromide at 25°-30°C. The reaction solution became turbid within a few minutes and showed a considerable crystalline deposit after standing 3 A days. The mixture was warmed VA hours on the steam bath in a loosely-stoppered flask, then cooled and filtered. The filtrate was washed twice with water and the benzene layer evaporated at diminished pressure. The liquid residue was dissolved in alcohol, shaken with charcoal and filtered. Addition to the filtrate of 0.3 gram of 85% phosphoric acid in alcohol gave a clear solution which, when seeded and rubbed, yielded 6-allyl-6,7-dihydro-5H-dlbenz[c,e] azepine phosphate, MP about 211°-215°C with decomposition.  [c.117]

A mixture of 750 grams of 1-methyl-3-benzoyl-4-hydroxy-4-phenylpiperidine and 2,500 cc of 48% hydrobromic acid is refluxed for about 20 minutes. It is then poured into 8 liters of water. An oily precipitate appears which on standing crystallizes. It is filtered and crystallized from about 3.5 liters of alcohol. 2-Methyl-9-phenyl-2,3-dihydro-1-pyridindene hydrobromide, MP 201°-203°C, is obtained.  [c.1204]

Ethyl-2-methyl-3-(10,11) -dihydro-5H-dibenzo [a,d] cycloheptene-5-ylidene)-1 -pyrrolinium iodide (4.7 g) was dissolved in 7 cc of methanol. To this solution there were added 1.4 g of sodium boron hydride within about 80 minutes with stirring and stirring of the solution was continued for two hours to complete the reaction. The reaction mixture was acidified with 10% aqueous hydrochloric acid solution and then the methanol was distilled off. The residual solution was alkalized with 20% aqueous sodium hydroxide solution and extracted with ether. The ether layer was dried over magnesium sulfate and the ether was distilled off. The resulting residue was further distilled under reduced pressure to yield 2.0 g of 1-ethyl-2-methyl-3-(10,11 ) dihydro-5H-dibenzo[a,d]cycloheptene-5-ylidene)pyrrolidine (boiling point 167°C/4 mm Hg.).  [c.1256]

To the oily residue containing ethyl 1-ethyl-1,4-dihydro-4-oxo-7-(4-pyridyl)-3-quinolinecar-boxylate was added excess 10% aqueous sodium hydroxide solution and ethanol, and the solution was heated on a steam bath for forty-five minutes to hydrolyze the ethyl ester to the corresponding carboxylic acid. The alkaline solution was diluted to a volume of about 500 ml with water, decolorizing charcoal was added and the mixture filtered. The filtrate was neutralized with acetic acid whereupon the carboxylic acid separated as a solid. The solid was collected and dried in a rotary evaporator. The solid was boiled with ethanol, the solution chilled and the resulting solid collected. The solid was recrystallized from dimethylformamide (about 150 ml) using decolorizing charcoal. The filtrate was chilled, diluted with about one-half volume of ethanol and the separated crystalline product was collected, recrystallized again from dimethylformamide and dried in vacuo to yield 4.3 g 1 -ethyl-1,4-di-hydro-4-oxo-7-(4-pyridyl)-3-quinolinecarboxylic acid, melting point 272°C to 273°C raised by further recrystallization to 290°C.  [c.1365]


See pages that mention the term Abietic acid, dehydro : [c.45]    [c.306]    [c.195]    [c.190]    [c.197]    [c.333]    [c.117]    [c.1182]   
The logic of chemical synthesis (1989) -- [ c.381 ]