7-methoxy-2-phenyl- -perchlorate perchloric acid

To a solution of 1.5 mmol of KDA, prepared from potassium lerl-butoxide, diisopropylamine and butyl-lithium, in 7 mL of diethyl ether is added dropwise, under an argon atmosphere, a solution of 0.293 g (1 mmol) of (/ )-2-methoxy-2-phenyl-l-[( )-3-phenyl-2-propenyloxy]propane in 2 mL of diethyl ether at — 100 °C (liquid nitrogen/methanol). After stirring for 5 h the resulting dark-red suspension is treated with a solution of 0.284 g (2 mmol) of iodomethane in 1 mL of diethyl ether. The mixture is stirred until the red color disappears (about 2 h). Then, the bath is removed and 5 mL of phosphate buffer (pH 7) are added, the mixture is extracted with ethyl acetate several times. The extracts are washed with aq NaCl, dried over MgS04, and concentrated. The residue is purified by TLC on silica gel to give (7 )-2-methoxy-2-phenyl-1-[(ii)-3-phenyl-l-butenyloxy]propane yield 0.232 g (75%). This is hydrolyzed to 3-phenylbutanal by treatment with aq perchloric acid (40 %)/diethyl ether. 

Methoxy-2-phenyl-l-benzotellurinium Perchlorate1 1.81 g (5.0 mmol) of 7-methoxy-2-phenyl-4-oxo-4H-1 -benzotellurin are dissolved in 20 ml] of dry tetrahydrofuran, the solution is cooled to — 78°, and 5.5 ml] of a 20% solution of diisobutyl aluminum hydride in hexane are added dropwise via a syringe. The resultant mixture is then slowly warmed to 20°, 20 m/] of a 1.0 molar sodium hydroxide solution are added, the mixture is stirred at 20° for 1 h, and is then poured into 100 ml] of diethyl ether. The organic phase is washed with brine, dried with anhydrous sodium sulfate, filtered, and concentrated. The residue is dissolved in 25 ml] of acetic acid, 2 ml] of 70% perchloric acid are added, and the solution is allowed to cool. The resultant red precipitate is filtered off, washed with several portions of diethyl ether, and air-dried yield 1.13 g (50%) m.p. 150° (dec). 

In connection with the elucidation of the structures of the products obtained upon reaction of the tropone (496) with perchloric acid, the 6-methoxy-substituted derivatives have been prepared by reaction of (496) with methyl iodide and silver fluoroborate. -Comparison of u.v. spectra indicated that the salts between the tropones (496) and perchloric acid were 6-hydroxy-derivatives of the perchlorate of (497). U.v. and n.m.r. spectra of the systems (496)—(499) are discussed and their properties and reactivities compared with the corresponding JV-phenyl-pyrrole analogue. A preliminary report of the polarographic, i.r., and u.v. spectroscopic properties, as well as the dipole moments, of both the C-annelated systems (496) and (497) without methyl groups in the thiophen ring and also the ion (500) with alkyl, hydroxy, and methoxy-groups in the seven-membered ring has been published. Values of piirR+ between 6 and 7 have been obtained for this system. The spectroscopic properties of metallocene derivatives such as (501)—(503) have also... 

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