Refrigerator mother

The study of stressful life events is a nice example of the type of variable studied in the second domain of environmental measures mentioned previously. Psychologists have for years studied the influences of a wide variety of life events, family interaction patterns, etc., under the hypothesis that they were proximal causal variables with regard to a variety of psychological outcomes. The now discredited hypothesis of the refrigerator mother is a classic example. 

Cooling is carried out by whatever coolant is selected and run through the annulus between the inner and outer pipe. Coolants may be cooling tower water, chilled brines, evaporating refrigerants, mother liquor stripped of crystals, or a combination of these. 

Mix together in a 250 ml. flask carrying a reflux condenser and a calcium chloride drying tube 25 g. (32 ml.) of freshly-distilled acetaldehyde with a solution of 59-5 g. of dry, powdered malonic acid (Section 111,157) in 67 g. (68-5 ml.) of dry pyridine to which 0-5 ml. of piperidine has been added. Leave in an ice chest or refrigerator for 24 hours. Warm the mixture on a steam bath until the evolution of carbon dioxide ceases. Cool in ice, add 60 ml. of 1 1 sulphuric acid (by volume) and leave in the ice bath for 3-4 hours. Collect the crude crotonic acid (ca. 27 g.) which has separated by suction filtration. Extract the mother liquor with three 25 ml. portions of ether, dry the ethereal extract, and evaporate the ether the residual crude acid weighs 6 g. Recrystallise from light petroleum, b.p. 60-80° the yield of erude crotonic acid, m.p. 72°, is 20 g. 

Phthalide. In a 1 litre bolt-head flask stir 90 g. of a high quality zinc powder to a thick paste with a solution of 0 5 g. of crystallised copper sulphate in 20 ml. of water (this serves to activate the zinc), and then add 165 ml. of 20 per cent, sodium hydroxide solution. Cool the flask in an ice bath to 5°, stir the contents mechanically, and add 73-5 g. of phthalimide in small portions at such a rate that the temperature does not rise above 8° (about 30 minutes are required for the addition). Continue the stirring for half an hour, dilute with 200 ml. of water, warm on a water bath imtil the evolution of ammonia ceases (about 3 hours), and concentrate to a volume of about 200 ml. by distillation vmder reduced pressure (tig. 11,37, 1). Filter, and render the flltrate acid to Congo red paper with concentrated hydrochloric acid (about 75 ml. are required). Much of the phthalide separates as an oil, but, in order to complete the lactonisation of the hydroxymethylbenzoic acid, boil for an hour transfer while hot to a beaker. The oil solidifles on cooling to a hard red-brown cake. Leave overnight in an ice chest or refrigerator, and than filter at the pump. The crude phthalide contains much sodium chloride. RecrystaUise it in 10 g. portions from 750 ml. of water use the mother liquor from the first crop for the recrystaUisation of the subsequent portion. Filter each portion while hot, cool in ice below 5°, filter and wash with small quantities of ice-cold water. Dry in the air upon filter paper. The yield of phthalide (transparent plates), m.p. 72-73°, is 47 g. 

In Texas, subterranean sulfate brines are pumped to the surface where the brines are first saturated with NaCl before they are cooled by mechanical refrigeration to form Glauber s salt (7,8). This salt is then separated from its mother Hquor, melted, and dehydrated with mechanical vapor recompression evaporators (9). 

The mother liquor is returned to the refrigerator and a second and a third crop of crystals may be collected after 24 and... 

The mother liquorsand washings of fractions I and II are concentrated froma volume of about 1.7 liters to 250 ml, the pH is adjusted to 2.5 with 100% formic acid and the solution is stored overnight in a refrigerator, whereby further substance crystallizes. This is filtered off under suction and washed with a small amount of water. The residue on the suction filter is azeotropically distilled with ethanol. There is obtained solid, almost colorless title substance which is denoted as 8. 8 is purer than A according to thin-layer chromatography. 

In dim red light, the weighed hydrazide contained in one of the 500 ml flasks (ca. 67 g 95% of theory) is washed into a 1000 ml beaker with 263 ml IN hydrochloric acid. 239 ml distilled water, 239 ml ethanol (95%), and 37 ml 2,4-pentanedione are added, and the well-mixed solution left to stand in the dark at room temperature until the reaction is complete, i.e., about 30 minutes. The reaction mixture is neutralized with the addition of 263 ml 1 N sodium hydroxide, and the beaker covered with parafilm and refrigerated to ensure complete precipitation. The pyrazole is filtered at the pump, the mother liquor being returned to the beaker and used to wash out the last few crystals, washed with cold water, and sucked dry under a stream of dry nitrogen. The product is dried in vacuo over barium oxide or phosphorus pentoxide for at least twelve hours before proceeding to the next step, wherein anhydrous conditions will increase yield. Hofmann calls for drying the pyrazole in vacuo at 60°, which indicated the product to be fairly stable. So all the hydrazide is converted prior to aminization. 

A. 3,3-Pmtamethylenediaziridine. A solution of 147 g. (1.5 moles) of cyclohexanone in 400 ml. of 15iV aqueous ammonia (6.0 moles) in a 1-1. beaker is stirred mechanically and cooled to 0° with an ice-salt mixture. Maintaining the temperature of the solution between 0° and - -10°, 124 g. (1.0 mole) of 90% hy-droxylamine-O-sulfonic acid (Note 1) is added in portions of about 1 g. The addition requires about 1 hour, and the mixture is stirred for mother hour at 0° and allowed to stand overnight at —15° in a refrigerator. The precipitated crystalline cake is filtered and pressed tight with a glass stopper. The solid is washed with 50-ml. portions of ice-cold ether, toluene, and finally ether. There is obtained 110-115 g. of product which is 70-90% pure (Notes 2 and 3). The product is divided into two portions, each of which is boiled briefly with a 50-ml. portion of toluene the solutions are decanted from small salt residues and cooled to 0° for 2 hours. The precipitates are filtered with suction and washed with 50 ml. of ice-cold petroleum ether. The combined yield of 3,3-pentamethylenediaziridine is 68-78 g. (61-70%), m.p. 104-107°. The purity is 96-100% (Note 4). 

In a 1-1. four-necked flask (or a three-necked flask with a Y-tube connector) equipped with a mechanical stirrer, a reflux condenser, a dropping funnel, and a thermometer are placed 208 g. (1.00 mole) of benzalacetophenone (Note 1), 60 g. (58.5 ml., 0.50 mole) of acetophenone, and 350 ml. of 1,2-dichloroethane. The contents of the flask are warmed to 70-75°, and 160 ml. of a 52% ethereal solution of fluoboric acid (Note 2) is added from the funnel with stirring during 30 minutes. With the first addition the mixture becomes orange subsequently the color changes to brownish yellow. After the addition is completed, the mixture is stirred and heated under reflux for 1 hour (Note 3). The fluorescent mixture is allowed to stand overnight in a refrigerator. The crystalline product that separates is collected on a Buchner funnel and washed well with ether. By addition of 250 ml. of ether (Note 4) to the mother liquor an additional quantity of 2,4,6-triphcnylpyrylium tctrafluoroboratc is obtained. A total yield of 125 135 g. (63 68%) of yellow crystals... 

In a 1-1. round-bottomed flask are placed 74 g. (0.5 mole) of phthalic anhydride and 30 ml. (0.5 mole) of freshly distilled monoethanolamine. The mixture is heated on a steam bath for 30 minutes the initial reaction is vigorous (Note 1). The reaction mixture is cooled to room temperature, and a reflux condenser is attached to the flask. To the cooled reaction mixture is added slowly, with shaking, 32 ml. (91.3 g., 0.337 mole) of freshly distilled phosphorus tribromide. The reaction flask is then placed on a steam bath and heated under reflux with occasional shaking for 1.25 hours (Note 2). The hot liquid reaction mixture is poured with stirring onto 750 g. of crushed ice. When the ice has melted completely, the crude /3-bromoethylphthali-mide is collected on a Buchner funnel, washed with cold water, and allowed to dry for a few minutes. The crude product (Note 3) is dissolved in 1.2 1. of aqueous ethanol (50% by volume) with the aid of heat. If necessary a small amount of 95% ethanol is added to effect complete solution. The hot solution is filtered and cooled in a refrigerator. A white crystalline product weighing 94-99 g. is obtained. Concentration of the mother liquor to 400 ml. yields an additional 1-3 g. of product. The total yield of product is 95-102 g. (75-80%) m.p. 80-82°. 

The checkers found it convenient to crystallize the viscous distillate from 125 ml. of methanol by chilling a hot solution in the refrigerator overnight. A small second crop amounting to about 2 g. may also be obtained by concentration of the mother liquors. 

Into a flask containing an ice-cold solution of 166.0 gm (2.0 moles) of valeronitrile and 90 ml (2.2 moles) of anhydrous methanol in 750 ml of anhydrous diisopropyl ether is bubbled dry hydrogen chloride until 78 gm (2.2 moles) is absorbed. The flask is stoppered, placed in the refrigerator for 48 hr, filtered of the white crystals, and the mother liquor concentrated to afford a combined yield of 240 gm (79 %) of methyl imidovalerate hydrochloride (after washing with fresh diisopropyl ether, and drying under reduced pressure). 

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