Phase sodium aluminum chloride

Dehydrochlorination of chlorinated derivatives such as 1,1,2-trichloroethane may be carried out with a variety of catalytic materials, including Lewis acids such as aluminum chloride. Refluxing 1,1,2-trichlorethane with aqueous calcium hydroxide or sodium hydroxide produces 1,1-dichloroethylene in good yields (22), although other bases such as magnesium hydroxide have been reported (23). Dehydrochlorination of the 1,1,1-trichloroethane isomer with catalytic amounts of a Lewis acid also yields 1,1-dichloroethylene. Other methods to dehydrochlorinate 1,1,1-trichloroethane include thermal dehydrochlorination (24) and by gas-phase reaction over an alumina catalyst or siUca catalyst (25). 

The Reissert reaction of 3,4-dihydro-p-carboline (213) has also been studied 47,48). It has been shown that 3,4-dihydro-p-carboline (213) afforded 1-cyano-2,9-dibenzoyl-l,2,3,4-tetrahydro-P-carboline (214) with a phase-transfer catalyst and trimethylsilyl cyanide (Scheme 27). However, the normal Reissert product 2-benzoyl-l-cyano-l,2,3,4-tetrahydro-p-carboline (215) was obtained when a catalytic amount of anhydrous aluminum chloride was used in addition to the trimethylsilyl cyanide reagent. Reaction of 214 with sodium... 

Triphenylphosphine sulfide 158 A mixture of thiophosphoryl chloride (50.7 g, 0.3 mole), aluminum chloride (133 g, 1 mole), and benzene (150 g, 1.92 moles) is heated, with stirring, to reflux. Evolution of hydrogen chloride begins at once and is complete after about 8 h. The mixture is poured on ice, and the aqueous phase is washed three times with benzene. The benzene phase and the benzene extracts are united and dried over sodium sulfate. After removal of the solvent there remains a residue (91 g) which, on two recrystallizations from aqueous acetone, gives the sulfide (75.5 g, 85.8% calculated on PSC13), m.p. 158-158.5°. 

Aluminum occurs widely in nature in silicates such as micas and feldspars, complexed with sodium and fluorine as cryolite, and in bauxite rock, which is composed of hydrous aluminum oxides, aluminum hydroxides, and impurities such as free silica (Cotton and Wilkinson 1988). Because of its reactivity, aluminum is not found as a free metal in nature (Bodek et al. 1988). Aluminum exhibits only one oxidation state (+3) in its compounds and its behavior in the environment is strongly influenced by its coordination chemistry. Aluminum partitions between solid and liquid phases by reacting and complexing with water molecules and anions such as chloride, fluoride, sulfate, nitrate, phosphate, and negatively charged functional groups on humic materials and clay. 

The precipitated succinimide is collected on a large Buchner funnel atop a 2-1. filter flask and is washed with six 50-ml. portions of methylene chloride. The lower organic layer in the filtrate is separated from the aqueous phase, which is extracted with two 25-ml. portions of methylene chloride. The organic layer and the extracts are combined, washed vigorously with 50 ml. of a 5% sodium hydroxide solution (Note 5) and three 80-ml. portions of water, and dried over 10 g. of anhydrous sodium sulfate for several hours in a flask wrapped with aluminum foil (Note 6). 

Hydroxytelluraxanthene 1.5 g(39 mmol) of lithium aluminum hydride is suspended in 100 ml of absolute diethyl ether, 9.24 g (30 mmol) of thoroughly ground teiluraxanthone are added in small portions to the stirred suspension kept at 20°, and the resultant mixture is stirred for 2 h. 100 ml of ethyl acetate are then added to the cooled, vigorously stirred reaction mixture, followed by a saturated aqueous ammonium chloride solution. The hydrolyzed mixture is filtered, the organic layer is separated, the aqueous phase is extracted twice with diethyl ether, and the organic solutions are combined, washed with water, dried with anhydrous sodium sulfate, filtered, and evaporated. The residue is chromatographed on aluminum oxide with benzene as the mobile phase yield 7.2 g (77%) m.p. 110 112°. 

The transformation takes place in the gas phase, in the presence of a supported mercuric chloride base catalyst in general, at a temperature between 100 and 170°C, and a pressure of about 03.106 Pa absolute. The support is activated charcoal, but this can be replaced by graphite, aluminum and sodium silicate etc. 

The dione adduct 25 (440 mg) and aluminum isopropoxide (1.83 g) were dissolved in dry isopropanol (8 mL). The mixture was boiled gently, and acetone and isopropanol were distilled slowly from the reaction mixture through a short column. From time to time isopropanol was added to maintain a constant volume. After one hour no more acetone could be detected in the distillate. The reaction mixture was then concentrated under reduced pressure, treated with ice-cold 2 N hydrochloric acid, and extracted with methylene chloride/ether (1 3). The organic phase was washed with sodium bicarbonate and saturated sodium chloride solution, and concentrated. The residue was crystallized twice from acetone/ether, to give 230 mg of colorless lactone 26. 

A more cost-effective and reliable route to 464 uses lactamides 465 or 467 as the precursor [95,117] (Scheme 67). These are readily available from lactamides 6c and 466 by standard inexpensive benzylation conditions (benzyl chloride, sodium hydride) or phase-transfer conditions (benzyl chloride, sodium hydroxide, tricaprylmethylammonium chloride, 92% yield). These alkylations, which have also been performed with / -chlorobenzyl chloride and / -methoxybenzyl chloride, proceed with no racemization. Reduction of lactamides 465 or 467 with sodium bis(2-methoxyethoxy)aluminum hydride (Vitride) furnishes (/S)-2-benzyl-oxypropanal (464) in high yield. The aldehyde itself is not very stable, and has a propensity to hydrate, so it should be used immediately after preparation. 

---