Ethereal salts

A 1-L, oven-dried, round-bottomed flask equipped with a magnetic stirrer is charged with 9.92 g (27.9 mmol) of methyl R)-3-(tert-butyldiphenylsilyloxy)-2-methylpropionate and 200 mL of dry hexanes (Note 15). The solution is cooled to -78°C, and 31.5 mL (31.5 mmol) of 1 M diisobutylaluminum hydride (in hexane) (DIBAL-H) (Note 16) is added dropwise over 15 min via a syringe pump. After the addition is complete, the resultant solution is stirred at -78°C for 2 hr. The reaction is quenched by pouring the cold solution info 250 mL of saturated aqueous Rochelle s salt. Ether (300 mL) and HjO (75 mL) are added and the biphasic mixture is stirred vigorously for 1 hr (Note 17). The layers are separated and the ether layer is washed with brine. The aqueous layer is extracted with ether (2 x 50 mL) and the combined extracts are dried over Na2S04. Filtration of the solution and concentration of the filtrate under reduced pressure followed by purification of the crude product by flash chromatography (Note 18) yields 7.85 g (86%) of (R)-3-(tert-bUtyldiphenylsilyloxy)-2-methylpropanal as a white solid (Note 19). 

The kinetic results discussed in the preceding paragraphs were supplemented by the data derived from conductance studies, namely those yielding the pertinent dissociation constants of ion-pairs, Kdiss. Plots of tfnKdlss vs. 1/T are curved for many salt-ethereal solvent systems, as exemplified by Fig. 46. At very low temperatures they are flat but become steeper as the temperature rises281,282,288,303,309,324, etc). This behavior is accounted for by the following equilibria2835 ... 

Azulenium salts. Ethereal fluoroboric acid added dropwise with stirring and ice-cooling under anhydrous conditions to a soln. of 4,6,8-trimethylazulene in abs. ether, benzaldehyde added to the resulting 4,6,8-trimethylazulenium fluoro-borate, and the product isolated after ca. 4 hrs. l-benzylidene-4,6,8-trimethyl-azulenium fluoroborate. Y 94%.— Azulenes can be converted into azulenium salts, which are derivatives of the tropenium cation, as well as into azuleniate salts, which are derivatives of ihe cyclopentadienyl anion. F. e. and reactions s. K. Hafner, H. Pelster, and J. Schneider, A. 650, 62 (1961) syntheses via azuleniate salts s. A. 650, 80. 

CH OfiSj, H2C(S03H)2- a colourless, crystalline solid which readily absorbs water vapour decomposes on distillation. The potassium salt is prepared by heating methylene chloride with an aqueous solution of potassium sulphite under pressure at 150-I60" C. The free acid is obtained by decomposing the sparingly soluble barium salt with sulphuric acid. The aryl esters are very stable, but the alkyl esters decompose on heating to give ethers. Resembles malonic acid in some of its reactions. 

Substances are generally soluble in like solvents. Organic molecules in molecular solvents such as CCI4, C2H5OH, ether, propanone. Inorganic salts are often soluble in water and less soluble in organic solvents. 

If triphenylmethyl chloride in ether is treated with sodium, a yellow colour is produced due to the presence of the anionic spiecies PhsC". Alternatively, if triphenylmethyl chloride is treated with silver perchlorate in a solvent such as THF, the triphenylmethyl cation is obtained. More conveniently, triphenylmethyl salts, PhsC X", can be obtained as orange-red crystalline solids from the action of the appropriate strong acid on triphenylcarbinol in ethanoic or propanoic anhydride solution. The perchlorate, fluoroborate and hexafluoro-phosphate salts are most commonly used for hydride ion abstraction from organic compounds (e.g. cycloheptatriene gives tropylium salts). The salts are rather easily hydrolysed to triphenylcarbinol. 

The hydrophilic parts can contain oxygenated groups (glycol ether types) or amines. The first detergents used amine and phosphoric acid salts or... 

Collidine 2i5 d carboxylic acid. Boil a mixture of 5 g. of the ester (II) and 50 ml. of 15% ethanolic potash under reflux for 30 minutes. The dipotassium salt crystallises during the boiling and during the subsequent cooling. Filter off the potassium salt at the pump and wash it with a small quantity of ethanol. Dilute the filtrate with about an equal volume of ether to precipitate a further small crop of the salt. Yield of combined crops 4 5 g. from 5 g. of the estei (I). 

The isolation of an aliphatic acid from its aqueous solution, particularly in the presence of metallic salts, is a tedious operation (cf. p. 56), although a few such acids, e.g., succinic acid, can be extracted with ether. Since, however, a solution of an acid or one of Its salts is admirably suited for most of the tests in this series, the isolation of the free acid is rarely necessary except as a nieans of distinguishing (as in (i)) between aliphatic and aromatic members. 

Oxonium salt formation. Shake up 0 5 ml. of ether with 1 ml. of cone. HCl and note that a clear solution is obtained owing to the formation of a water-soluble oxonium salt. Note that aromatic and aliphatic hydrocarbons do not behave in this way. In general diaryl ethers and alkyl aryl ethers are also insoluble in cone. HCl. 

By cooling the solution in a freezing mixture (ice and salt, ice and calcium chloride, or solid carbon dioxide and ether). It must be borne in mind that the rate of crystal formation is inversely proportional to the temperature cooling to very low temperatures may render the mass... 

In the isolation of organic compounds from aqueous solutions, use is frequently made of the fact that the solubility of many organic substances in water is considerably decreased by the presence of dissolved inorganic salts (sodium chloride, calcium chloride, ammonium sulphate, etc.). This is the so-called salting-out effect. A further advantage is that the solubility of partially miscible organic solvents, such as ether, is considerably less in the salt solution, thus reducing the loss of solvent in extractions. 

Absolute diethyl ether. The chief impurities in commercial ether (sp. gr. 0- 720) are water, ethyl alcohol, and, in samples which have been exposed to the air and light for some time, ethyl peroxide. The presence of peroxides may be detected either by the liberation of iodine (brown colouration or blue colouration with starch solution) when a small sample is shaken with an equal volume of 2 per cent, potassium iodide solution and a few drops of dilute hydrochloric acid, or by carrying out the perchromio acid test of inorganic analysis with potassium dichromate solution acidified with dilute sulphuric acid. The peroxides may be removed by shaking with a concentrated solution of a ferrous salt, say, 6-10 g. of ferrous salt (s 10-20 ml. of the prepared concentrated solution) to 1 litre of ether. The concentrated solution of ferrous salt is prepared either from 60 g. of crystallised ferrous sulphate, 6 ml. of concentrated sulphuric acid and 110 ml. of water or from 100 g. of crystallised ferrous chloride, 42 ml. of concentrated hydiochloric acid and 85 ml. of water. Peroxides may also be removed by shaking with an aqueous solution of sodium sulphite (for the removal with stannous chloride, see Section VI,12). 

---