Potassium mantle

The carbonyl compound to be reduced (0.1 mole) is placed in a 250-ml round-bottom flask with 13.5 g of potassium hydroxide, 10 ml of 85% hydrazine hydrate, and 1(X) ml of diethylene glycol. A reflux condenser is attached and the mixture is heated to reflux for I hour (mantle). After refluxing 1 hour, the condenser is removed and a thermometer is immersed in the reaction mixture while slow boiling is continued to remove water. When the pot temperature has reached 200°, the condenser is replaced and refluxing is continued for an additional 3 hours. The mixture is then cooled, acidified with concentrated hydrochloric acid, and extracted with benzene. The benzene solution is dried, and the benzene is evaporated to afford the crude product, which is purified by recrystallization or distillation. 

A mixture of cyclohexanone (11.8 g, 0.12 mole), ethylene glycol (8.2 g, 0.13 mole), /j-toluenesulfonic acid monohydrate (0.05 g), and 50 ml of benzene is placed in a 250-ml round-bottom flask fitted with a water separator and a condenser (drying tube). The flask is refluxed (mantle) until the theoretical amount of water (approx. 2.2 ml) has collected in the separator trap. The cooled reaction mixture is washed with 20 ml of 10 % sodium hydroxide solution followed by five 10-ml washes with water, dried over anhydrous potassium carbonate, and filtered. The benzene is removed (rotary evaporator) and the residue is distilled, affording l,4-dioxaspiro[4.5]decane, bp 65-67713 mm, 1.4565-1.4575, in about 80% yield. 

A 500-ml, three-necked, round-bottom flask is equipped with a condenser, a dropping funnel, and a thermometer in the reaction mixture. In the flask is placed a mixture of 85% hydrazine (115 ml, 118 g) and 225 ml of 95% ethanol with a few boiling chips. The solution is brought to reflux (mantle) and cinnamaldehyde (100 g, 0.76 mole) is added dropwise over about 30 minutes followed by an additional 30 minutes of refluxing. A still head is attached to the flask and volatiles (ethanol, water, hydrazine hydrate) are slowly distilled at atmospheric pressure until the pot temperature reaches 200° (about 3 hours). Hereafter, phenylcyclopropane is collected over the range 170-180°. When the pot temperature exceeds 250°, the recovery is complete. The crude product (55-65 g) is washed twice with 50-ml portions of water and dried (anhydrous potassium carbonate). Distillation under vacuum through a short column affords the product, bp 60°/13 mm, 79-80°/37 mm, n f 1.5309, about 40 g (45%). 

Five grams of potassium hydroxide (85% KOH) is dissolved in 100 ml. of Methyl Cellosolve (Note 1) in a 500-ml. flask (Note 2) fitted with a mechanical stirrer, reflux condenser, and a heating mantle. Dicyandiamide (50.4 g. 0.6 mole) (Note 3) and benzo-nitrile (50 g. 0.485 mole) are added, and the mixture is stirred and heated. A solution is formed, and, when the temperature reaches 90-110°, an exothermic reaction begins and the product separates as a finely divided white solid. The vigor of the reaction is kept under control by the refluxing of the solvent (Note 4). 

The reaction is carried out in a 500-ml. three-necked flask equipped with a reflux condenser, mechanical stirrer, heating mantle, and nitrogen inlet. The equipment is similar to that pictured in Fig. 11, except that an addition funnel is not required. In the reaction flask 20 g. (0.36 mol, 100% excess) of potassium hydroxide is dissolved in 300 ml. of absolute ethanol. The spare neck is closed with a ground-glass stopper, and the solution is stirred until it reaches room temperature. Addition of the carborane to the warm basic solution may result in an initial vigorous reaction. To this solution is added 30.0 g. (0.175 mol) of solid dimethylcarborane. The solution is stirred for one hour at room temperature and is then heated at the reflux temperature for 14 hours or until hydrogen evolution has stopped. 

C. (R,R)-N,N -Bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine. A 2-L, three-necked, round-bottomed flask equipped with a mechanical overhead stirrer, reflux condenser, and an addition funnel is charged with 29.7 g of (R,R)-1,2-diammoniumcyclohexane mono-(+)-tartrate salt (0.112 mol), 31.2 g of potassium carbonate (0.225 mol, 2 eq), and 150 mL of water. The mixture is stirred until dissolution is achieved, and 600 mL of ethanol is added. The cloudy mixture is heated to reflux with a heating mantle and a solution of 53.7 g (0.229 mol, 2.0 eq) of 3,5-di-tert-butylsalicylaldehyde in 250 mL of ethanol is then added in a slow stream over 30 min (Note 19). The addition funnel is rinsed with 50 mL of ethanol and the mixture is stirred at reflux for 2 hr before heating is discontinued. Water, 150 mL, is added and the stirred mixture is cooled to <5°C over 2 hr and maintained at that temperature for another hour. The yellow solid is collected by vacuum filtration and washed with 100 mL of ethanol. After the solid is air dried, it is dissolved in 500 mL of methylene chloride. The organic solution is washed with 2 x 300 mL of water, followed by 300 mL of saturated aqueous sodium chloride. The organic layer is dried over sodium sulfate, and filtered to remove the drying agent. The solvent is removed by rotary evaporation to yield the product as a yellow solid, mp 200-203°C (Notes 20 and 21). 

Nielsen SG, Rehkamper M, Brandon AD, Norman MD, Turner S, O Reilly SY (2007) Thallium isotopes in Iceland and Azores lavas - Implications for the role of altered crust and mantle geochemistry. Earth Planet Sd Lett 264 332-345 Nier AO (1950) A redetermination of the relative abundances of the isotopes of carbon, nitrogen, oxygen, argon and potassium. Phys Rev 77 789... 

C. 3,6,9-Tns(p-toly/sul/ony/)-3,6,9-friazaundecane-l,ll-dioZ (3). A 2-1., three-necked, round-bottomed flask is equipped with a mechanical stirrer, thermometer, reflux condenser, and heating mantle. In the flask are placed 226 g. (0.40 mole) of triamine 1, 77.5 g. (0.88 mole) of ethylene carbonate (Note 1), and 0.7 g. of powdered potassium hydroxide. The stirred mixture is heated at 160-170° for 4 hours (Note 3). The reaction mixture is then allowed to cool to 90°, and 500 ml. of methanol is added through... 

The reaction is conducted in a 100-mL stainless-steel autoclave containing a glass insert. The autoclave is stirred magnetically and heated with an electrical mantle. The purification was carried out with standard Schlenk techniques, under purified nitrogen. The methanol was distilled over potassium methanolate and saturated with nitrogen prior to use.11... 

Method A. Huang-Minlon modification of the Wolff-Kishner reduction. Place 36.0 g (0.3 mol) of redistilled acetophenone, b.p. 201 °C, 300 ml of diethylene glycol, 30ml of 90 per cent hydrazine hydrate (CAUTION) and 40g of potassium hydroxide pellets in a 500-ml two-necked round-bottomed flask fitted with a reflux condenser insert a thermometer supported in a screw-capped adapter in the side-neck so that the bulb dips into the reaction mixture. Warm the mixture on a boiling water bath until most of the potassium hydroxide has dissolved and then heat under reflux for 1 hour either by means of a free flame or by using a heating mantle. Remove the reflux condenser and fit a still-head and condenser for downward distillation. Distil until the temperature of the liquid rises to 175 °C (1). Separate the upper hydrocarbon layer from the distillate and extract the aqueous layer twice with 20 ml portions of ether. Dry the combined upper layer and ethereal extracts with magnesium sulphate, remove the ether on a water bath and distil the residue. Collect ethylbenzene at 135-136 °C the yield is 20 g (62.5%). 

There is little doubt that the Tuscany mafic magmas have been subject to fractional crystallisation, mixing and crustal assimilation (e.g. Conticelli 1998). However, their high MgO, Ni and Cr concentrations, whose values are close to those of primary mantle melts, exclude that the mafic magmas with different enrichments in potassium and incompatible elements can be derived from each other by any common evolution process. Therefore, it has been concluded that the variable petrological and geochemical compositions of mafic rocks in Tuscany basically result from anomalous and heterogeneous mantle sources (Peccerillo et al. 1987). 

The variable compositions of mafic rocks at likely reflect the occurrence of different types of parental liquids, which are characterised by distinct enrichment in potassium and incompatible elements. The positive correlation of potassium vs. incompatible elements and the lack of systematic differences in isotopic compositions between potassic and ultrapotas-sic rocks are suggestive of a magma genesis by different degrees of partial melting in a broadly common mantle source. This is supported by the similar REE and incompatible element patterns of all the mafic rocks (Fig. 4.8). Also the melilite-bearing rocks from Montefiascone share these... 

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