Aluminum recrystallization temperature

The dry tosylhydrazone (20 g, 45.5 mmol) is dissolved in 750 ml of 1,2-dimethoxyethane (freshly distilled from lithium aluminum hydride) in a flame-dried 1 liter round bottom flask fitted with a 240 ml addition funnel, a drierite tube and a magnetic stirrer. A 2.05 M ether solution of methyllithium (130 ml, Alfa Inorganics, Inc.—Caution to avoid the mineral oil impurity the methyllithium solution is decanted from a cold solution which contains a precipitate) is placed in the dropping funnel and added over a 60 min period. The temperature of the reaction mixture increases to ca. 35° during the addition however, no cooling precautions are required. The highly colored reaction mixture is stirred for 7 hr and then poured into 1.5 liters of ice water. The flocculent precipitate is digested for 12 hr at room temperature to speed the filtration. After filtration the filter cake is washed with 500 ml water and dried under vacuum at 50° for several hr. The androsta-5,16-dien-3l5-ol is obtained in ca. 70% yield after recrystallization from methanol mp 138-139°. 

To a stirred solution of 45g 3,5-dimethoxybenzoyl chloride and 17.4g thiophen in 300 ml benzene at 0° C, add dropwise 10.5g freshly distilled stannic chloride. Stir one hour at room temperature and add 200 ml 3% aqueous HC1. Separate the benzene layer and wash the aqueous layer with benzene. Dry and evaporate in vacuum the combined benzene layers and distill the red residue (250° C bath/4.5) to get 45g 2-(3,5-dimethoxybenzoyl) thiophen(I). Recrystallize from petroleum ether. Add a solution of 21 g AICI3 in 160 ml ether to a stirred suspension of 6.1 g lithium aluminum hydride in 140 ml ether. After 5 minutes add a solution of 39g(I) in 300 ml ether at a rate giving a gentle reflux. Reflux and stir 1 hour cool in an ice bath and treat dropwise with 50 ml water, then 50 ml 6N aqueous sulfuric acid. Separate the layers, extract the aqueous layer with 3X100 ml ether and dry, evaporate in vacuum the combined ether layers. Can distill the residue (230° C bath/5mm) to get 27g oily 2-(3,5-dimethoxybenzyl) thiophen (II). Recrystallize from petroleum ether. Reflux a solution of 5g (II) in 700 ml ethanol with W-7 Raney Nickel prepared from Ni-Al alloy (see Org. Synthesis Coll. Vol 111,176(1955)) for 6 hours. Filter, evaporate in vacuum and can distill (140/0.01) to get about 2.2g oily olivetol dimethyl ether which can be reduced to olivetol as described elsewhere here. -... 

Convert indole to indolyl-3-methyl-ketone (I) by treating indolyl-Mg-Br (preparation already described) with acetyl-Cl, by treating indole in POCl3 with dimethylacetamide (Vilsmeier reaction), or by reacting indole with diketene (ACS 22,1064(1968)). 15.9 g (1) in 50 ml methanol cool, stir and add dropwise 16 g Br2. Reflux 1 Vi hours on water bath cool, filter, wash with ether and recrystallize-methanol to get 18 g indolyl-3-Br-methyl-ketone (II). Dissolve 11.9 g (II) in 60 ml warm isopropanol and add 11 g 3 8% aqueous DMA (or equimoiar amount other amine) reflux one hour on water bath. Filter (recrystallize-ethanol) to get 8.5 g indolyl-3-dimethylamino-methyl ketone (III). Add 4.6 g (0.02 M) (III) in 30 ml tetrahydrofuran to 2.3 g lithium aluminum hydride in 50 ml tetrahydrofuran, stir one-half hour at room temperature and reflux two hours. Add a little water dropwise and extract the precipitate with acetone. Dry, evaporate in vacuum the combined organic phases to get an oil which will precipitate with ether-petroleum ether to give DMT. (Ill) should be tested for psychedelic activity. Dialkyltryptamines BCSJ 11,221 (1936), BSC 2291 (1966)... 

B (Alternative) 20 g of the unrefluxed precipitate (ethyl-ester of (1)) from last part of step A in 100 ml ether. Add dropwise to a solution of 4 g lithium aluminum hydride in 900 ml ether at 0°. Reflux three hours and isolate the resulting tryptophol as described earlier. Dissolve 3 g of the tryptophol in 140 ml ether and stir at 0°. Add dropwise 1.8 g PBr3 in 30 ml ether and let stand sixteen hours at room temperature. Decant the ether and wash the precipitate with ether. Wash ether w ith water, NaHC03 and water, and dry, evaporate in vacuum the ether to get the bromide (recrystallize-ethanol). 2 g of the bromide and 1.5 g piperidine (or equimolar amount DEA. etc.) in 65 ml methanol and heat in sealed tube fifteen... 

Prepare 6-methoxy-l-indanone (I) (JCS 1986(1962)) using polyphosphoric acid made by diluting 500 g of the commercial acid with 120 g 85% phosphoric acid. 2.5 g (I) in 176 ml ether and reflux one hour with 0.27 g lithium aluminum hydride. Cool and carefully add water and filter when bubbling stops (can use Celite filter aid). Dry and evaporate in vacuum and store twelve hours at -15° (under N2 if possible) to precipitate the white 6-methoxy-l-indanol (II) (recrystallize-n-hexane). 2.5 g (II) in 73 ml benzene and reflux one-half hour with 0.2 g p-toluenesulfonic acid. Cool, add water and separate the phases. Extract the aqueous phase with ether and combine with benzene phase and dry, evaporate in vacuum to get 5-methoxy-indene (III) (can distill 110-45/10). 1.53 g (III) and 1.39 g N.N-diethyl-aminoethyl-Cl.HCI in benzene (prepare the free base in benzene as described previously). Reflux four hours with 0.42 g sodamide, cool, wash with water and dry, evaporate in vacuum to get the indene analog of 6-methoxy DET as a dark liquid (can crystallize as oxalate). Alternatively, dissolve 2.51 g (III) in ether and treat (under N if possible) with 12 ml 1.6M buty-Li in hexane at 0-10°. After two hours cool to -30° and add 12 ml more of butyl-Li. Add ether suspension of 2.5 g N,N-diethylaminoethyl-CI. HCI over one-half hour and warm to room temperature. Filter, evaporate in vacuum to get the 6-methoxy-DET analog. 

This compound was prepared as depicted in Scheme 1 using the following procedure To a 250-ml round-bottom flask was added lO.OOg (0.0170mol) of 2,2-bis[4-( 1-naphthoxy)phenyl]hexafluoropropane (1), 5.71 g (0.0360mol) of 4-fluorobenzoyl chloride, 2.3 g (0.0246 mol) of dimethyl sulfone, and 132 g of dichloromethane. The mixture was stirred under nitrogen until the solids dissolved, then cooled in an ice bath, and 14.5 g (0.109 mol) of aluminum chloride was added. The mixture was stirred for 1 h at ice-bath temperature, 24 h at room temperature, and 1 h at reflux. The mixture was allowed to cool to room temperature and poured into methanol. The resulting solid was filtered, washed with methanol and water, dried, and recrystallized from DMAc to yield 11.6 g (82% yield), m.p. = 261-263°C. Calculated for C HM04F, C, 70.67 H, 3.39 F, 18.25. Found C, 70.74 H, 3.36 F, 18.54. 

Yttrium alloys have many applications. The metal doped with rare earths such as europium is used as phosphor for color television receivers. When added to iron, chromium, vanadium, niobium, and other metals it enhances resistance of these metals and their alloys to high temperature oxidation and recrystallization. It is a deoxidizer for vanadium and other nonferrous metals. Yttrium-aluminum garnets are used in lasers and in jewelery gemstones. Yttrium-iron garnets are used as transmitters and as transducers of acoustic energy. 

Methyl-2-aminobenzophenone can be prepared similarly by substituting toluene for benzene. The yield of crude material, m.p. 85-88°, is 70%. On recrystallization from 95% ethanol, using 5 ml. per g., there is obtained, in two crops, a 70% recovery of 4/-methyl-2-aminobenzophenone, m.p. 92-93°. Because of the higher temperature required in the steam distillation (cf. Note 5), the sulfonamide is obtained in a form difficult to purify. As a result the crude aminoketone usually contains 1-2 g. of aluminum oxide. 

While aromatic nitro and azoxy compounds have been reduced to azo compounds with lithium aluminum hydride, aliphatic nitro compounds produced only the corresponding aliphatic amines [65]. The usual technique involves dropwise addition of 1 mole of nitro compound in ether to 1.05-1.15 moles of lithium aluminum hydride in ether solution at Dry Ice temperatures followed by warming to room temperature. If the resulting product is only slightly soluble in ether, hydrolysis should be carried out with dilute sulfuric acid. Then the azo compound simply needs to be filtered off, washed with water, and dried. If the product is ether-soluble, the ether layer is separated, evaporated, and the residue is recrystallized [65, 66]. 

A mixture consisting of monochlorobenzene (33.1 g), /V-cthylcarbazole (0.11 mol), and zinc chloride (10 mmol) were heated at 80°C and treated with the dropwise addition of 4-fluoro-2-methylbenzoyl chloride (0.10 mol) and stirred for 1 hour. The mixture was cooled to ambient temperature and treated with -heptane (33.1 g) and then 16.5 ml of water added. The organic layer was isolated and neutralized with 8.30 ml of 1% aqueous sodium hydroxide and then washed with 40.0 ml of water in two portions. The mixture was concentrated to 50 ml and then treated with monochlorobenzene solution (90.0 g) and aluminum chloride (40.0 g) and cooled to 10°C. The solution was treated with acetyl chloride (0.13 mol), stirred at ambient temperature for 1 hour, and then poured into a mixture of dichloroethane (224 g) and 134 ml of ice water. The organic layer was collected and then treated with 40 ml 5% hydrochloric acid, 40 ml of water, and 40 ml 2% aqueous NaOH solution. It was and then concentrated, the residue recrystallized in -propyl acetate, and... 

To a suspension of 1 g of lithium aluminum hydride in 10 ml of anhydrous tetrahydrofuran cooled in an ice bath was added dropwise a solution of 1.94 g of methyl 3-methyl-trans-4a-cisoid-4a,5a-cis-5a-l,4a,5,5a,10b,10c-hexahydro-7-dioxino[5,4-a]cyclopenta[b]benzofurancarboxylate in 40 ml of anhydrous tetrahydrofuran. After being stirred for 30 min at room temperature, the reaction mixture was cooled in an ice bath. The excess of lithium aluminum hydride was decomposed by the addition of ethyl acetate, and aqueous saturated solution of potassium sodium tartarate was added to the reaction mixture. After filtration of the mixture, the filtrate was concentrated and the residue was dissolved in 10 ml of methanol. After addition of 2 g of potassium carbonate to the solution, the mixture was stirred for 3 hours at room temperature and was concentrated. After water was added to the residue, the aqueous mixture was extracted 3 times with ethyl acetate. The combined organic layers were washed with water and saturated aqueous solution of sodium chloride, dried, and concentrated to give 2 g of crude crystals. The crude crystals were recrystallized from ethyl acetate-hexane to yield 1.49 g of the pure crystals of the titled compound (m.p. 124-125°C, yield 85%). 

A solution of 8.2 g. (0.040 mole) of purified aluminum isopropoxide and 2.75 g. (0.011 mole) of 4-keto-l,2,3,4-tetrahydrochrysene in 25 cc. of dry toluene is refluxed for four hours, in an oil bath. After the solution has cooled slightly, 25 cc. of dry isopropyl alcohol is added to facilitate removal of acetone, the water is removed from the reflux condenser, and a water condenser set for downward distillation is attached to the top by means of a short bent tube (a Hahn partial condenser with a 1-cm. layer of isobutyl alcohol in the inner condensing tube may be used). The mixture is heated at such a rate that slow distillation occurs (2 to 5 drops per minute, the volume of solution should be maintained by further addition of solvent as needed). When the test for acetone is completely negative, f the toluene solution is cooled and the aluminum salt is decomposed with cold 10% sulfuric acid (from 5 cc. of concentrated sulfuric acid and 80 cc. of water). The product is separated with the toluene, and the solution is washed with dilute aqueous ammonia and water, and then evaporated at room temperature under a stream of air (solutions of secondary alcohols which are susceptible to dehydration should be evaporated at room temperature a stream of air should not be used with carbinols boiling below 200°). There is obtained 2.10 g. (76%) of colorless 4-hydroxy-l, 2,3,4-tetrahydrochrysene melting at 156-158°. Two recrystallizations from a mixture of benzene and petroleum ether bring the melting point to 160-162°. 

---