Solutions, formaldehyde Distillation

Weigh out accurately about 2 g. of glycine, transfer to a 250 ml. graduated flask, dissolve in distilled water, make up to the mark, and mix well. Transfer 25 ml. of the solution to a conical flask, add 2 drops of phenolphthalein, and then again add dilute sodium hydroxide very carefully until the solution is just faintly pink. No v add about 10 ml. (/. ., an excess) of the neutralised formaldehyde solution the pink colour of the phenolphthalein disappears immediately and the solution becomes markedly acid. Titrate with AI io sodium hydroxide solution until the pink colour is just restored. Repeat the process with at least two further quantities of 25 ml. of the glycine solution in order to obtain consistent readings. 

Ethyl propane-1 1 3 3-tetracarboxylate. Cool a mixture of 320 g. (302 ml.) of redistilled diethyl malonate and 80 g. of 40 per cent, formaldehyde solution ( formalin ) contained in a 1-htre round-bottomed flask to 5° by immersion in ice, and add 5 g. (7 ml.) of diethylamine. Keep the mixture at room temperature for 15 hours and then heat under a reflux condenser on a boiling water bath for 6 hours. Separate the aqueous layer, dry the organic layer with anhydrous magnesium sulphate, and distil under reduced pressure. Collect the ethyl 1 1 3 3-tetracarboxylate at 200-215°/20 mm. The yield is 250 g. 

In a 500 ml. three-necked flask, fitted with a reflux condenser and mechanical stirrer, place 121 g. (126-5 ml.) of dimethylaniline, 45 g. of 40 per cent, formaldehyde solution and 0 -5 g. of sulphanilic acid. Heat the mixture under reflux with vigorous stirring for 8 hours. No visible change in the reaction mixture occurs. After 8 hours, remove a test portion of the pale yellow emulsion with a pipette or dropper and allow it to cool. The oil should solidify completely and upon boiling it should not smell appreciably of dimethylaniline if this is not the case, heat for a longer period. When the reaction is complete, steam distil (Fig. II, 41, i) the mixture until no more formaldehyde and dimethylaniline passes over only a few drops of dimethylaniline should distil. As soon as the distillate is free from dimethylaniline, pour the residue into excess of cold water when the base immediately solidifies. Decant the water and wash the crystalline solid thoroughly with water to remove the residual formaldehyde. Finally melt the solid under water and allow it to solidify. A hard yellowish-white crystalline cake of crude base, m,p. 80-90°, is obtained in almost quantitative yield. RecrystaUise from 250 ml. of alcohol the recovery of pure pp -tetramethyldiaminodiphenylmethane, m.p. 89-90°, is about 90 per cent. 

Place 3 3oz packets of Mildewcide into a 1L flask with an electric heating mantle and cork in the neck connected to a gas bubbler immersed in at least 550mL of distilled water. Heat the paraformaldehyde (what is in the Mildewcide) to between 180-200C (a temp, regulator is absolutely necessary for this step or use a silicone oil bath). The paraformaldehyde will depolymerize making formaldehyde gas in about 91% yield. Alternatively, the gas can be bubbled through the Ammonia solution directly (only for the brave ). If the Formaldehyde solution will not be used immedi-... 

Novolak Resins. In a conventional novolak process, molten phenol is placed into the reactor, foHowed by a precise amount of acid catalyst. The formaldehyde solution is added at a temperature near 90°C and a formaldehyde-to-phenol molar ratio of 0.75 1 to 0.85 1. For safety reasons, slow continuous or stepwise addition of formaldehyde is preferred over adding the entire charge at once. Reaction enthalpy has been reported to be above 80 kj /mol (19 kcal/mol) (29,30). The heat of reaction is removed by refluxing the water combined with the formaldehyde or by using a small amount of a volatile solvent such as toluene. Toluene and xylene are used for azeotropic distillation. FoHowing decantation, the toluene or xylene is returned to the reactor. 

To 500 g. (3.85 moles) of freshly distilled ethyl acetoacetate in a i-l. flask set in ice and well cooled, are added 152 g. (2.0 moles) of 40 per cent aqueous formaldehyde solution and 20-25 drops of diethylamine. The flask and contents are kept cold for six hours and are then allowed to stand at room temperature for forty to forty-five hours. At the end of this time two layers are present, a lower oily layer and an upper aqueous layer. The layers are separated, and the aqueous layer is extracted with 50 cc. of ether. The ether solution is added to the oily layer, and the resulting solution is dried over 30 g. of calcium chloride. The ether is then removed by distillation on a steam bath. The residue, amounting to approximately 500 g., is diluted with an equal volume of alcohol and is thoroughly cooled in an ice bath. Ammonia is then passed into the mixture until the solution is saturated. This requires from four to eight hours, and during this time the flask is kept packed in ice. The ammoniacal alcoholic solution is allowed to stand at room temperature for forty to forty-five hours. Most of the alcohol is now evaporated the residue is cooled, and the solid i,4-dihydro-3,5-dicarbethoxy-2,6-dimethylpyridine is removed from the remaining alcohol on a suction filter. The dried ester melts at 175-180 and amounts to 4ro-435 g. (84-89 per cent of the theoretical amount). 

The amine, under the name N,N,N, N -tetramethyl-methylenediamine, may be purchased from Ames Laboratories, South Norwalk, Connecticut. The checkers prepared it by the following procedure. A solution of 60.7 g. (0.75 mole) of 37% aqueous formaldehyde solution is placed in an 800-ml. beaker equipped with a mechanical stirrer and thermometer, and cooled in an ice bath. Two hundred seventy-one grams (1.50 moles) of a 25% aqueous solution of dimethylamine is added to this solution at a rate such that the reaction temperature is kept below 15°. The solution is stirred for 30 minutes after the addition is complete, and potassium hydroxide pellets (approximately 150 g.) are added in portions until the reaction mixture separates into two layers. The upper layer is separated, dried over potassium hydroxide pellets overnight, and distilled to give 59 -64 g. (77-83%) of bis(dimcthylamin())mclliane, b.p. 83 84°. ... 

Meerwein s Ester (9) Dimethyl malonate (13.2 g, 0.4 mole) and 6 g of 40 % aqueous formaldehyde solution are mixed in an Erlenmeyer flask and cooled to 0° in an ice bath. To the mixture is added 0.3 g of piperidine and enough ethanol to produce a homogeneous solution. The solution is allowed to stand at 0° for 12 hours, at room temperature for 24 hours, and at 35 0° for 48 hours. The reaction product is washed with water (50 ml) followed by dilute sulfuric acid, then dried (sodium sulfate). Unreacted malonic ester is distilled off under vacuum leaving a residue of about 12.5 g, which contains methylenemalonic ester, methylenebismalonic ester, and hexacarbomethoxypentane. 

The following cheap procedure serves for the preparation of large amounts of methylamine hydrochloride (Brochet and Gambier, Bull. Soc. chim., 1895 [iii.], 13, 533). Heat together in a distilling flask attached to a downward condenser 250 g. of ammonium chloride and 570 c.c. of 35 per cent formaldehyde solution. With the thermometer in the liquid, slowly raise the temperature to 104° and maintain at this point until distillation ceases (about 4-5 hours from the start). By then 100-120 g. of water and methyl alcohol will have collected in the receiver. Cool the flask, remove the ammonium chloride which separates by filtration at the pump, and evaporate the filtrate to half its volume on the water bath. Again remove ammonium chloride by filtration and concentrate the filtrate until a film of crystals forms on the surface. Cool and separate the methylamine hydrochloride by Ultra-... 

The use of distilled formaldehyde, not formalin, which contains alcohol, is recommended. Freshly prepared paraformaldehyde can also be used, especially if large volumes of fixative are needed for perfusion fixation. To prepare an 8% solution of paraformaldehyde, in a fume hood add 2 g of paraformaldehyde (trioxymethylene) powder to 25 mL of deionized glass-distilled water. With constant stirring, heat solution to 60-70°C. Once the solution has reached the proper temperature, continue to stir for 15 min. The solution will be milky. Add one to two drops of 1 VNaOH, with stirring, until the solution clears. A slight miUdness may persist. Cool and filter through Whatman No. 1 filter paper. This solution should be used the same day that it is prepared. 

Methylamine Hydrochloride. 125 g of ammonium chloride and 250 g 40% aqueous formaldehyde solution are placed in a distilling apparatus, with the thermometer well below the surface of the liquid. The mixture is slowly heated to 104° and held at this temp until no more liquid distills. The product in the flask is cooled and filtered from ammonium chloride. The liquid is then evaporated on a water bath to half its original volume and a second crop of ammonium chloride is filtered off. The filtrate is concentrated at 10(T until a crystalline scum forms on the surface. On cooling methylamine hydrochloride separates and is removed by filtration. Further evaporation and cooling produces another crop of methylamine hydrochloride, which is also filtered. The combined yield is treated with boiling chloroform, filtering hot, washed with room temp chloroform, and dried in a vacuum desiccator. Yield 40 g. 

A freshly-opened supply of paraformaldehyde purchased from Aldrich Chemical Company, Inc. was used by the checkers. The use of commercial formaldehyde solutions which now contain up to 15% methanol leads to the formation of several by-products which cannot be separated by distillation from the a-(hydroxymethyl)acrylate. 

Racemic 4-(4-fluorophenyl)-l-methyl-l,2,3,6-tetrahydropyridine (50 g) was dissolved in a mixture of 21.6 ml of concentrated sulfuric acid and 50 ml of water. To the solution were added 25 ml of concentrated hydrochloric acid and 22.4 ml of 37% formaldehyde solution. The mixture was refluxed for 5 h, cooled, and 125 ml of concentrated ammonia were added. The mixture was extracted with 50 ml of toluene. Drying of the toluene solution and distillation gave 38 g of 4-(4-fluorophenyl)-3-hydroxymethyl-l-methyl-l,2,3,6-tetrahydropyridine with boiling point 110°-120°C at 0.1 mm Hg. 

Buffer Solution Phenol- phthalein Distilled Water IM Formaldehyde Solution Distilled Water... 

To a 20 mL Erlenmeyer flask, 1 mL of 0.15 M Tris-HCl buffer (pH 7.2), 0.1 mL of 0.2 M disodium EDTA, and 0.5 mL of liver homogenate were added. After preincubation for 5 minutes at 37°C, 0.4 mL of 0.5 M glycine was added. Shaking continued for 30 minutes before the reaction was terminated by adding 0.5 mL of 25% trichloroacetic acid. The reaction mixture was centrifuged and the supernate diluted fivefold with distilled water. To 0.1 mL of the supernate, 2.5 mL of distilled water, 0.4 mL of acetylacetone, and 1 mL of 10% formaldehyde solution were added. This mixture was heated for 10 minutes at 100°C and then kept in an ice bath until analysis of 20 fiL by HPLC. Product formed was linear with liver homogenate up to 0.5 mL, and with time up to 60 minutes. 

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