Magnesium ethoxy

A synthesis of XIV was accomplished as follows (9) /J-carboline-1-carboxylic acid chloride was condensed with the magnesium ethoxy derivative of malonic ester to yield, after acid hydrolysis, 4-hydroxy-canthin-6-one (XV). This compound, with phosphorous oxychloride followed by heating in a sealed tube with potassium methyl mercaptide, gave the alkaloid XIV. If 4-hydroxycanthin-6-one is condensed with phosphorous oxychloride-phosphorous pentachloride, 4,5-dichlorocan-thin-6-one and 4-hydroxy-5-chlorocanthin-6-one are formed. 

The third alkaloid from the Australian plant turned out to be 4-methylthiocanthin-6-one. Its chemistry paralleled that of the above bases. Oxidation yielded jS-carboUne-l-carboxylic acid, reduction gave canthin-6-one. It was synthesized as follows j8-carboline-l-carboxylic acid chloride was condensed with the magnesium ethoxy derivative of malonic ester to yield after hydrolysis 4-hydroxycanthin-6-one. This compound first treated with phosphorous oxychloride then reacted with potassium methyl mercaptide gave the alkaloid. 

To a mixture of 0.10 mol of 1-ethoxy-l,2-heptadiene (see this chapter, Exp. 13) and 120 ml of diethyl ether was added 1 g of copper(I) bromide. A solution of butyl magnesium bromide in about 200 ml of diethyl ether, prepared from 0.25 mol of butyl bromide (see Chapter II, Exp. 5) was added in 15 min. The reaction was weakly exothermic and the temperature rose slowly to about 32°C. The mixture was held for an additional 40 min at that temperature, then the black reaction mixture was... 

To a mixture of 25 ml of water and 3 ml of 95% sulfuric acid were added 40 ml of DMSO. The mixture was cooled to 10°C and 0.20 mol of l-ethoxy-l,4-hexadiyne (see Chapter III, Exp. 51) was added with vigorous stirring in 15 min. During this addition, which was exothermic, the temperature of the mixture was kept between 20 and 25 0. After the addition stirring was continued for 30 min at 3S C, then 150 ml of water were added and six extractions with diethyl ether were carried out. The combined extracts were washed with water and dried over magnesium sulfate. Evaporation of the solvent in a water-pump vacuum, followed by distillation through a 25-cm... 

Aza-3,4-benzo-5,6-dipropylpentatriafu]valene hydriodide (373) was obtained in 20% yield by the action of l,2-di-n-propyl-3-ethoxy-cyclopropenium fluoroborate on indole magnesium iodide in a methylene chloride-ether mixture. 

Bromo-6-m ethoxy naphthalene Ethyl bromoisobutyrate Magnesium Hydrogen... 

Direct preparation of azo compounds in good yields is accomplished by treatment of nitro compounds with lithium aluminum hydride [576], with magnesium aluminum hydride [577], with sodium bis(2-methoxy ethoxy)aluminum hydride [575], with silicon in alcoholic alkali [331] or with zinc in strongly alkaline medium [578], Hydrazobenzene was obtained by controlled hydrogenation of nitrobenzene in alkaline medium (yield 80%) [572] and by reduction with sodium bis 2-methoxyethoxy)alumium hydride (yield 37%) [544],... 

High yields of amines have also been obtained by reduction of amides with an excess of magnesium aluminum hydride (yield 100%) [577], with lithium trimethoxyaluminohydride at 25° (yield 83%) [94] with sodium bis(2-methoxy-ethoxy)aluminum hydride at 80° (yield 84.5%) [544], with alane in tetra-hydrofuran at 0-25° (isolated yields 46-93%) [994, 1117], with sodium boro-hydride and triethoxyoxonium fluoroborates at room temperature (yields 81-94%) [1121], with sodium borohydride in the presence of acetic or trifluoroacetic acid on refluxing (yields 20-92.5%) [1118], with borane in tetrahydrofuran on refluxing (isolated yields 79-84%) [1119], with borane-dimethyl sulflde complex (5 mol) in tetrahydrofuran on refluxing (isolated yields 37-89%) [1064], and by electrolysis in dilute sulfuric acid at 5° using a lead cathode (yields 63-76%) [1120]. 

Dehalogenation and related reactions have also been employed in the synthesis of many bicyclobutanes. Sodium induced dechlorination of l,3-dichloro-2,2,4,4-letramethylcyclobu-tane (69) gave 2,2,4,4-tetramethylbicyclo[1.1.0]butane (70) in 47% yield,29 while magnesium also converted l-chloro-3-ethoxy-l-phenyl-2,2,4,4-tetramethylcyclobutane (71) into 1-phenyl-2,2,4,4-tetramethylbicyclo[1.1.0]butane (72) in 40% yield.31 Other typical preparations are summarized in Table 3 25-29-31 35... 

A 1-M hexane solution of di isobutyl aluminum hydride (400 mL, 0.40 mol) (Note 10) is added dropwise with stirring at 0°C oxer a 1-hr period. The solution is stirred for 2 additional hr at 0°C. To quench the reaction 200 mL of methanol is carefully added to the stirred reaction mixture, followed slowly at first then more rapidly with 400 mL of water and then 300 mL of 10 sulfuric acidt solution. After the mixture is stirred for 10 min, it is transferred to a separatory funnel and 500 mL of 10% sulfuric acid solution is added. The separatory funnel is shaken vigorously for 5 min and the organic phase 1s separated. The aqueous phase is extracted four times with 300 mL of diethyl ether. The organic phases are combined and washed twice with 300 mL of saturated sodium bicarbonate solution, twice with 300 mL of water, twice with 300 mL of brine, and dried over magnesium sulfate. Solvent removal on a rotary evaporator followed by short path distillation at reduced pressure affords 31-34 g (40-44%, based on 3-ethoxy-6-methyl-2-cyclohexen-l-one) of 4-(E-l,2-dichlorovinyl )-4-methy 1-2-cyclohexen-l-one (1) as a colorless oil, bp 75-78°C (0.1 mm) (Note 11). 

Methyl-l-piperazinyl)benzimididazole (5.00 g) prepared as above is dissolved in N,N-dimethylformamide (50 ml) and thereto is added sodium hydride (concentration 50%) (1.50 g) at room temperature, and the mixture is stirred for 30 minutes. To the mixture is added 2-bromoethyl ethyl ether (4.00 g), and the mixture is stirred at 70°C for 10 hours. To the reaction mixture is added water (150 ml), and the mixture is extracted with ethyl acetate. The extract is washed with water, dried over anhydrous magnesium sulfate and then concentrated to give a brown oily substance (5.40 g). The brown oily substance is treated with fumaric acid (3.26 g) in hot ethanol. The crude crystals thus obtained are recrystallized from ethyl acetate-ethanol to give l-[2-(ethoxy)ethyl]-2-(4-methyl-l-piperazinyl)benzimidazole 3/2 fumarate (6.31 g) as colorless plates, melting point 167.5°-168.5°C. Elementary analysis for C22H30N4O7 Calcd. (%) C, 57.13 H, 6.54 N, 12.11 Found (%) C, 57.04 H, 6.44 N, 12.02. 

Trifluoromethyl)-2-(2-chloro)ethoxy-l-bromoethane (3-Trifluoromethyl)phenyl magnesium bromide is prepared under the normal conditions for magnesium derivatives, from 48.6 g of magnesium turnings and 455.7 g of (3-trifluoromethyl)bromobenzeneand 1.5 liters anhydrous ether. 

The hydrolytic condensation is conducted in an acid medium (in the presence of hydrochloric acid) therefore, it is accompanied by the destruction of ethoxy magnesium chloride formed ... 

Ri [2-Ethoxycarbonylphenyltelluro] Selenium4 To a solution of 1.1 g (2.0 mmol) of bis[2-ethoxy-carbonylphenyl] ditellurium in 50 ml of pyridine are added 0.20 g (1.8 mmol) of finely powdered selenium dioxide, the mixture is heated with stirring at 80° for 30 min, cooled, then poured into 250 ml of ice/water. This mixture is extracted with two 50 ml portions of chloroform, the extracts are combined, washed with three 100 mi portions of water, dried with anhydrous magnesium sulfate, filtered, and evaporated. The residue is recrystallized from hexane/benzene yield 0.5g (45%) m.p. 147°. 

XIX, was developed by Hoshino and Kobayashi (37). The reaction of 5-ethoxy-V-methyltryptamine (XVIII) with ethyl magnesium iodide... 

Nakazaki (43) has recently described the synthesis of 1,2-dehydro-2-ethoxy-9-methylbisnordeoxyeseroline (XXXVI), effected by the means illustrated in structures XXXV and XXXVI. The Grignard compound prepared from 2,3-dimethylindole and methyl magnesium iodide was treated with chloroacetonitrile to give the indolenine XXXV. 

Methylmagnesium bromide Magnesium, bromomethyl- (8,9) (75-16-1) Diisopropylamine (8) 2-Propanamine, N-(l-methylethyl)- (9) (108-18-9) 2-Methyi-i-tetralone 1 (2H)-Naphthalenone, 3,4-dihydro-2-methyl- (8,9) (1590-08-5) Cyclopropanone ethyl hemiketal Cyclopropanol, 1-ethoxy- (8.9) (13837-45-1) Sodium hydride (8,9) (7646-69-7)... 

A recent report describes the use of magnesium (2-ethoxy)ethoxide as an additive in reactions to prepare organolithium reagents. The additive moderates the basicity of the prepared anion and prevents unwanted side reactions, for example with the solvent. 

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