Triphenylmethyl-potassium

Potassium triphenylmethyl, KCPhg. —1. Triphenylmethane and metallic j otassium are heated at 200° to 220° C. in an indifferent atmosphere. By this method the compound is stated to be red, and when treated with benzyl chloride to yield a[Pg.8]

The compound has a similar appearance and the same properties as the sodium deri ative. It exhibits, however, this difference, that whilst sodium triphenyl is unstable in the presence of ammonia, the potassium compound is stable even at 100° C. Moreover, it has not been found possible to synthesise the triphenylmethyl group by the action of triphenylmethyl chloride on potassium triphenylmethyl. 

C24H2,BN402 144873-97-2) see Losartan potassium 5 -0-(triphenylmethyl)thymidine 3 -methanesulfonate (CjoH,0N2O7S 42214-24-4) see Zidovudine... 

When 2-methoxy-l,6-methano[10]annulene 32 was subjected to a cyclopropana-tion with diazomethane and cuprous chloride as catalyst reaction occurred preferentially at the 5,6-, 6,7- and/or 1,10-bonds and the adducts spontaneously underwent disrotatory opening yielding the corresponding methoxybicyclo[5.4.1]dodecapen-taenes. Hydride abstraction with triphenylmethyl fluoroborate was performed on the mixture and the ions 33 and 34 so produced were treated with dilute aqueous potassium hydroxide. The annulenones 13 and 14 were then separated by chromatography. 

Triphenylmethyl sodium and triphenylmethyl potassium conduct in liquid ammonia although they slowly react with that solvent.887 888 When the liquid ammonia is allowed to evaporate from a solution of triphenylmethyl sodium in ammonia, the residue is a colorless mixture of sodamide and triphenylmethane. The sodium-tin and sodium-germanium compounds analogous to sodium triphenylmethide are also strong electrolytes in liquid ammonia. Sodium acetylide in liquid ammonia is dissociated to about the same extent as sodium acetate in water.889... 

Triphenylsilyl potassium adds like triphenylmethyl sodium to formaldehyde, giving the expected alcohol. 

Another differential reaction is copolymerization. An equi-molar mixture of styrene and methyl methacrylate gives copolymers of different composition depending on the initiator. The radical chains started by benzoyl peroxide are 51 % polystyrene, the cationic chains from stannic chloride or boron trifluoride etherate are 100% polystyrene, and the anionic chains from sodium or potassium are more than 99 % polymethyl methacrylate.444 The radicals attack either monomer indiscriminately, the carbanions prefer methyl methacrylate and the carbonium ions prefer styrene. As can be seen from the data of Table XIV, the reactivity of a radical varies considerably with its structure, and it is worth considering whether this variability would be enough to make a radical derived from sodium or potassium give 99 % polymethyl methacrylate.446 If so, the alkali metal intitiated polymerization would not need to be a carbanionic chain reaction. However, the polymer initiated by triphenylmethyl sodium is also about 99% polymethyl methacrylate, whereas tert-butyl peroxide and >-chlorobenzoyl peroxide give 49 to 51 % styrene in the initial polymer.445... 

R = BOM, = MOM. (TMS = trimethylsilyl, KHMDS = potassium hexamethyidisilazide, MOM = methoxymethyl, DIBAL-H = diisobutylaluminium hydride, Tr = triphenylmethyl, DMAP = 4-N,N-dimethylaminopyridine, TBAE = tetrabutylammonium fluoride, BOM = benzyloxym ethyl)... 

However, when m-DNB was added to a solution of triphenylchloromethane and potassium tcrt-butylate in 2,2-dimethoxypropane, the yield of the substitution product and dimer of the triphenylmethyl radical markedly increased and decreased, respectively (Simig and Lempert 1979). Therefore, the main pathway of the reaction does not involve the ion-radical step. These authors suggested an alternative pathway, which is conformed by a thorough structural analysis of the secondary products formed along with tert-butyl ester of triphenylcarbinole (Huszthy et al. 1982a, 1982b) (Scheme 4.21). 

Using both a carbocyanine dye and another lipophilic cation, triphenylmethyl-phosphonium, Seligmann and Galhn found defective changes in the membrane potential in PMNs from patients with chronic granulomatous disease in response to FMLP or PMA, In PMNs from patients with other disorders of function the responses were normal. The resting membrane potential, the response to valinomycin, (an ionophore for potassium) and the response to the ionophore for Ca, were all normal or only slightly impaired. 

A 1-Pyrroline V-oxides dimerize readily in alkaline media.335 Different products are obtained on treatment of 2,2-dimethyl-d1-pyrroline V-oxide with sodamide or triphenylmethyl sodium.338 Sodium-potassium alloy in ethylene glycol produces a derivative of 1, r-dihydroxy-2,2 -dipyrrolidyl.337... 

Cleavage of 1,1,1-triphenylmethyl ketones, 1,1,1-Triphenylmethyl ketones are cleaved to carboxylic acids and triphenylmethane by potassium t-butoxide (6 equiv.) and H2O (2 equiv.) in ether (equation I). This combination of reagents had previously been used by Gassman and co-workers to hydrolyze amides. For the preparation of triphenylmethyl ketones, see Organolithium compounds, this volume. 

Schlenk and Marcus in 1914 found that triphenylmethyl chloride reacted with sodium amalgam in dry ether solution, when the operation was carried out in an atmosphere of nitrogen. The resulting compound, sodium triphenylmethyl, was a brick-red mass, decomposed by moisture or carbon dioxide. Kraus and Kawamura in 1928 showed that triphenylmethyl chloride reacts with sodium and potassium in liquid ammonia, but that the potassium compound is more stable than the sodium derivative. A number of compounds similar in structure to triphenylmethyl have since been sho wn to give similar reactions. Rubidium and esesium also form similar derivatives. ... 

Two equivalents of potassium are allowed to react with triphenylmethyl chloride in liquid ammonia. 

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