Potassium-44, magnetic

Typically, dry potassium nitrate is pulverized in a ball mill. Sulfur is milled into cellular charcoal to form a uniform mix in a separate ball mill. The nitrate and the sulfur—charcoal mix are screened and then loosely mixed by hand or in a tumbling machine. Magnetic separators may be used to ensure the absence of ferrous metals. The preliminary mix is transferred to an edge-mimer wheel mill with large, heavy cast iron wheels. A clearance between the pan and the wheels is required for safety purposes. The size of this gap also contributes to the density of the black powder granules obtained. Water is added to minimize dusting and improve incorporation of the nitrate into the charcoal. The milling operation requires ca 3 to 6 h. 

The ESR spectrum of the pyridazine radical anion, generated by the action of sodium or potassium, has been reported, and oxidation of 6-hydroxypyridazin-3(2//)-one with cerium(IV) sulfate in sulfuric acid results in an intense ESR spectrum (79TL2821). The self-diffusion coefficient and activation energy, the half-wave potential (-2.16 eV) magnetic susceptibility and room temperature fluorescence in-solution (Amax = 23 800cm life time 2.6 X 10 s) are reported. 

B. (l-Azido-3,3-dimethoxy-l-propenyl)benzene. In a 2-1., one-necked, round-bottomed flask equipped with a magnetic stirrer and powder funnel are placed 156 g. (0.45 mole) of the iodoazide from Part A and 1500 ml. of anhydrous ether. The solution is stirred and cooled in an ice-salt bath (— 5° to 0°), and 62 g. (0.55 mole) of potassium <-butoxide (Note 6) is added. The powder funnel is then replaced by a calcium chloride drying tube and the mixture is stirred for 4 5 hours at 0°. At the end of this time 350 ml. of water is added while the mixture is still cold. The ethereal layer is then separated and washed with three 350-ml. portions of water and dried over magnesium sulfate. The solvent is removed with a rotary evaporator without heating, leaving 67-75 g. (68-76%) of (l-azido-3,3-dimethoxy-l-propenyl)-benzene as a dark oily liquid (Note 7). This material can be used without further purification for Part C (Note 8). 

A solution consisting of 27.6 g. (0.2 mole) of p-dimethoxybenzene (Note 6), 4.0 g. of potassium hydroxide, and 400 ml. of methanol is placed in the apparatus. The beaker and contents are cooled with a 0° bath. The solution is electrolyzed with magnetic stirring for 6 hours at a current intensity maintained at 2.0 A (Notes 5, 7). The temperature of the solution varies between 8 and 14°. During this time small amounts of methanol are added from time to time to compensate for evaporation. 

Chlorooctane (14 9 g, 0 I mol), potassium fluoride dihydrate (47 g, 0 5 mol), hexadecyltributylphosphonium bromide (5 1 g, 0 01 mol), and water (30 mL) are mixed in an autoclave equipped with a magnetic stirrer and heated to 160 °C (bath temperature) for 7 h After this time gas-liquid chromatographic analysis (10% Carbowax 20M on Chromosorb) shows a 95% conversion to a mixture of 1-fluorooctane (82%), octenes (6%), and 1-octanol (7%) The organic layer is separated, washed with water, washed with concentrated sulfuric acid, washed once again with water, dried over calcium chloride, and distilled to give 10 g (77%) of ] -fluorooctane... 

The oxidizing agent is prepared in a 500-ml flask equipped with a magnetic stirrer and cooled in an ice bath as follows In the flask are placed 60 ml of concentrated sulfuric acid and 20 ml of water, and the solution is cooled to 10°. Potassium persulfate (42 g, 0.15 mole) is added slowly to the stirred solution while maintaining the temperature below 10°. The solution is diluted with an additional 65 ml of water maintaining the temperature below 15°. The solution is now cooled to about 7° and 0.08 mole of the ketone is added over 40 minutes. After the addition has been completed, the solution is allowed to come to room temperature and stirring is continued for 20 hours. The solution is diluted carefully with 150 ml of water and extracted twice with 75-ml portions of ether. The ether is washed with sodium bicarbonate solution, followed by water, and the ethereal solution is dried. Removal of the solvent, followed by fractional distillation, affords the product ester. 

A dry 5(X)-mI flask equipped with a thermometer, pressure-equalizing dropping funnel, and magnetic stirrer is flushed with nitrogen and then maintained under a static pressure of the gas. The flask is charged with 50 ml of tetrahydrofuran and 13.3 ml (0.15 mole) of cyclopentene, and then is cooled in an ice bath. Conversion to tricyclo-pentylborane is achieved by dropwise addition of 25 ml of a 1 M solution of diborane (0.15 mole of hydride see Chapter 4, Section 1 for preparation) in tetrahydrofuran. The solution is stirred for 1 hour at 25° and again cooled in an ice bath, and 25 ml of dry t-butyl alcohol is added, followed by 5.5 ml (0.05 mole) of ethyl bromoacetate. Potassium t-butoxide in /-butyl alcohol (50 ml of a 1 M solution) is added over a period of 10 minutes. There is an immediate precipitation of potassium bromide. The reaction mixture is filtered from the potassium bromide and distilled. Ethyl cyclopentylacetate, bp 101730 mm, 1.4398, is obtained in about 75% yield. Similarly, the reaction can be applied to a variety of olefins including 2-butene, cyclohexene, and norbornene. 

In a dry, 250 ml, three-necked flask equipped with a dropping funnel and magnetic stirrer are placed 40 ml of dry /-butyl alcohol (distilled from calcium hydride) and 4.0 g (0.036 mole) of potassium /-butoxide. The solution is cooled in ice and 40 g (49 ml, 0.49 mole) of dry cyclohexene is added. Bromoform (10 g, 3.5 ml, 0.039 mole) is added to the cooled, stirred reaction vessel dropwise over about hour, and the vessel is stirred an additional hour with the ice bath removed. The reaction mixture is poured into water (approx. 150 ml), and the layers are separated. The aqueous layer is extracted with 25 mi of pentane, and the extract is combined with the organic layer. The combined layers are dried (sodium sulfate), and the solvent is removed. The product is purified by distillation, bp 10078 mm. 

A 500-ml flask is equipped with a condenser and a magnetic stirrer and charged with 175 ml of water, 18 ml ofTHF, lOg of potassium carbonate, 6.5 g of silver nitrate, and 10 g of 1-bromoadamantane. The mixture is heated in a boiling water bath for 1 hour with stirring, cooled, and the crystallized 1-adamantanol is collected by filtration. It may be purified by dissolving it in THF and diluting the solution with water. The product has mp 289-290°. 

Pipette 25 mL of the solution containing magnesium, manganese and zinc ions (each approx. 0.02M), into a 250 mL conical flask and dilute to 100 mL with de-ionised water. Add 0.25 g hydroxylammonium chloride [this is to prevent oxidation of Mn(II) ions], followed by 10 mL of the buffer solution and 30-40 mg of the indicator/potassium nitrate mixture. Warm to 40 °C and titrate (preferably stirring magnetically) with the standard EDTA solution to a pure blue colour. 

For demonstrations add to a 1 -L beaker, 600 mL water, 60 mL cone, sulfuric acid, 20 g malonic acid, 7.8 g potassium bromate, 0.7-0.8 g (NHj ),Ce(NCL), and about 1 mL 0.025 M [Fe(phen)i]S04 ( ferroin indicator) to give a visible color. Stir magnetically. A short but variable length of time can be expected before oscillations begin their frequency depends on the temperature. 

To the solution is added 900 ml. of water, and the resulting mixture is washed with four 500-ml. portions of ether. The ether layers are combined and washed with 200 ml. of aqueous 10% potassium carbonate and then twice with 200-ml. portions of water (Note 9). The ether layer is dried for 1 hour over 200 g. of anhydrous calcium chloride (Note 10) and the solvent is removed on a rotary evaporator at room temperature to give 145-158 g. of crude product (Note 11). Distillation under reduced pressure through a Vigreux column gives 115-128 g. of a fraction, b.p. 83-86° (54 mm.), w22 d 1.4620-1.4640, containing 95% of l-bromo-3-methyl-2-butanone as established by proton magnetic resonance measurements (Note 11). 

A. Piperidine-4-spiro-5 -hydantoin (1). A 1000-mL, single-necked, round-bottomed flask equipped with a magnetic stirbar and an addition funnel fitted with an argon inlet is charged with 4-piperidone monohydrate hydrochloride (30.0 g, 195 mmol), ammonium carbonate (41.3 g, 420 mmol), 250 mL of methanol, and 150 mL of deionized water (Note 1). The mixture is allowed to stir at room temperature until all solids dissolve and then a solution of potassium cyanide (26.7 g, 410 mmol) (Note 2) in 100 mL... 

C. 4-Amino-l-tert-butyloxycarbonylpiperidine-4-carboxylic acid (3). A 2000-mL, round-bottomed flask equipped with a magnetic stirbar is charged with a suspension of the hydantoin 2 (40.0 g, 0.8 mol) in 340 mL of THF (Note 12), and 340 mL of 2.0M potassium hydroxide solution (Note 13) is added in one portion. The flask is stoppered and the reaction mixture is stirred for 4 hr (Note 14) and then poured into a 1000-mL separatory funnel. The layers are allowed to separate over 45 min and the aqueous layer is then drained into a 1000-mL round-bottomed flask. This solution is cooled at 0°C while the pH is adjusted to 8.0 by the slow addition of ca. 100 mL of 6.0N HC1 solution. The resulting solution is further acidified to pH 6.5 by slow addition of 2.0 N HC1 solution (Note 15). The white precipitate which appears is collected by filtration on a Buchner funnel and the filtrate is concentrated to a volume of 60 mL to furnish additional precipitate which is collected by filtration. The combined portions of white solid are dried at room temperature under reduced pressure (65°C 0.5 mm) for 12 hr and then suspended in 100 mL of chloroform (Note 16) and stirred for 45 min. The white solid is filtered and then dried under reduced pressure (85°C 0.5 mm) for 24 hr to yield 13.4-14.1 g (64-68%) (Note 17) of the amino acid 3 as a white solid (Note 18). 

FIGURE L.2 The apparatus typically used for a titration magnetic stirrer flask containing the analyte clamp buret containing the titrant—in this case, potassium hydroxide. 

The spectral properties of benzobarrelene are as follows infrared (potassium iodide) cm. strong peaks 1460, 1325, 790, 750, 690, 660 proton magnetic resonance (chloroform-d) S (multiplicity, number of protons, assignment) 4.9 (multiple , 2, bridgehead H), 6.8-7.3 (multiple , 8, aryl and vinyl H). The reported melting point is 65.5-66°.From 20 g. of tetrachlorobenzo-barrelene the submitters obtained 8.3-8.8 g. (79-83%) of benzobarrelene, m.p. 64-65°. 

C. Active magnesium. A 200-ml., three-necked, round-bottomed flask is equipped with a Teflon-coated magnetic stirring bar, stopper, rubber septum, and condenser connected to an argon inlet (Note 6). The flask is charged with 1.5 g. (0.038 mole) of freshly cut potassium (Notes 7 and 8), 2.01 g. (0.0211 mole) of anhydrous magnesium chloride (Note 9), 3.55 g. (0.0214 mole) of anhydrous potassium iodide (Note 10), and 50 ml. of tetrahydrofu-ran (Note 11). The mixture is stirred vigorously (Note 12) and... 

A. trans-l,2-Cyclohexanediol. In a 100-ml., round-bottomed flask equipped with a reflux condenser protected with a drying tube are placed a magnetic stirring bar, 17.56 g. (0.0667 mole) of thallium (I) acetate (Note 1), and 40 ml. of dried acetic acid (Note 2). The mixture is stirred and heated at reflux for 1 hour. To the cooled mixture are added 2.84 g. (3.5 ml., 0.0346 mole) of cyclohexene (Note 3) and 8.46 g. (0.0333 mole) of iodine (Note 4). The resulting suspension is stirred and heated at reflux for 9 hours (Note 5), and then cooled to room temperature. The yellow precipitate of thallium(I) iodide is filtered and washed thoroughly with ethyl ether. The filtrates are comhined, the solvents are removed under reduced pressure with a rotary evaporator (Note 6), and the residual liquid is dissolved in dry ethyl ether. The turbid solution is dried with anhydrous potassium carbonate, and the solvent is again removed by rotary evaporation (Note 6), affording 5.4-6.3 g. of trans-1,2-cyclohexanediol diacetate as a mobile, brown liquid (Note 7). 

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