Aluminum chloride borohydride

Lithium borohydride reacted with aluminum chloride to produce aluminum borohydride (7). 

Olsen, L., and R. T. Sanderson The Reaction of Aluminum Chloride with Lithium Borohydride. J. Inorg. Nucl. Chem. 7, 228 (1958). 

ALUMINUM BOROHYDRIDE ALUMINUM BROMIDE ALUMINUM CHLORIDE ALUMINUM FLUORIDE ALUMINUM IODIDE ALUMINUM OXIDE ALUMINUM SULFATE ARGON ARSENIC... 

Synthesis ofLysergic Acid, By reacting N-benzoyl-3-(B-carboxyethyl)-dihydroindole (see JCS, 3158 (1931) for the preparation of this compound) with thionyl chloride, followed by aluminum chloride gives l-benzoyl-5-keto-l,2,2a,3,4,5-hexahydrobenzindole. This is then brominated to give the 4-bromo-derivative, which is converted to the ketol-ketone by reacting with methylamine acetone ethylene ketol. This is then hydrolized by acid to yield the diketone and treated with sodium methoxide to convert it to the tetracyclic ketone. Acetylate and reduce this ketone with sodium borohydride to get the alcohol, which is converted to the hydrochloride form, as usual. 

A boron analog - sodium borohydride - was prepared by reaction of sodium hydride with trimethyl borate [84 or with sodium fluoroborate and hydrogen [55], and gives, on treatment with boron trifluoride or aluminum chloride, borane (diborane) [86. Borane is a strong Lewis acid and forms complexes with many Lewis bases. Some of them, such as complexes with dimethyl sulfide, trimethyl amine and others, are sufficiently stable to have been made commercially available. Some others should be handled with precautions. A spontaneous explosion of a molar solution of borane in tetrahydrofuran stored at less than 15° out of direct sunlight has been reported [87]. 

Transformation of ketones to alcohols has been accomplished by many hydrides and complex hydrides by lithium aluminum hydride [55], by magnesium aluminum hydride [89], by lithium tris tert-butoxy)aluminum hydride [575], by dichloroalane prepared from lithium aluminum hydride and aluminum chloride [816], by lithium borohydride [750], by lithium triethylboro-hydride [100], by sodium borohydride [751,817], by sodium trimethoxyborohy-dride [99], by tetrabutylammonium borohydride [771] and cyanoborohydride [757], by chiral diisopinocampheylborane (yields 72-78%, optical purity 13-37%) [575], by dibutyl- and diphenylstannane [114], tributylstanrume [756] and others Procedure 21, p. 209). 

Reduction of carbonyl to methylene in aromatic ketones was also achieved by (dane prepared from lithium aluminum hydride and aluminum chloride [770], by soditim borohydride in triiluoroacetic acid [841 with triethylsilane in trifluoroacetic acid [555, 777], with sodium in refluxing ethanol [842], with zinc in hydrochloric acid [843] and with hydrogen iodide and phosphorus [227], geiibrally in good to high yields. 

Reduction of aromatic carboxylic acids to alcohols can be achieved by hydrides and complex hydrides, e.g. lithium aluminum hydride 968], sodium aluminum hydride [55] and sodium bis 2-methoxyethoxy)aluminum hydride [544, 969, 970], and with borane (diborane) [976] prepared from sodium borohydride and boron trifluoride etherate [971, 977] or aluminum chloride [755, 975] in diglyme. Sodium borohydride alone does not reduce free carboxylic acids. Anthranilic acid was reduced to the corresponding alcohol by electroreduction in sulfuric acid at 20-30° in 69-78% yield [979],... 

Borane prepared by adding aluminum chloride to a solution of sodium borohydride in diethylene glycol dimethyl ether (diglyme) reduced aliphatic and aromatic esters to alcohols in quantitative yields in 3 hours at 25° using a 100% excess, or in 1 hour at 75° using a 25% excess of lithium borohydride over 2 mol of the hydride per mol of the ester [738] Procedure 20, p. 209). 

Glacial acetic acid. Aluminum foil. Toluene, Methylene iodide. Acetonitrile, Tetrahydrofuran, Sodium hydroxide. Acetone, Magnesium sulfate. Aluminum chloride. Chloroform Ethylenediamine, Glyoxal, Sodium nitrite. Hydrochloric acid. Nitric acid. Ethanol 4,4,4-Trinitrobutryaldehyde, Methanol, Sodium borohydride. Hydrochloric acid. Methylene chloride. Sodium bicarbonate. Magnesium sulfate... 

The use of activated anthranihc acid derivatives facUitates the preparation of the amides in those cases where the amines are either umeactive or difficult to obtain. Thus, reaction of (87-1) with phosgene gives the reactive the isatoic anhydride (89-1). Condensation of that with ortho-toluidine leads to the acylation product (89-2) formed with a simultaneous loss of carbon dioxide. This is then converted to the quinazolone (89-3) by heating with acetic anhydride. Reaction with sodium borohydride in the presence of aluminum chloride selectively reduces the double bond to yield the diuretic agent metolazone (89-4) [99]. 

Acylmetallocenes undergo many reactions shown by acylbenzenes (35, 87, 91, 116, 124), but a detailed discussion is not presented here. Reductions with either lithium aluminum hydride or sodium borohydride give the corresponding carbinols, while Clemmensen reduction, reduction with lithium aluminum hydride plus aluminum chloride, catalytic hydrogenation, etc., yield corresponding alkyl derivatives. Acetylferrocenes undergo a variety of base condensation reactions and can be oxidized to ferrocenecarboxylic acids without apparent oxidation of the iron atom. 

Ruoho and Rong have descnbed a shorter route to salmeterol (Scheme 4). Friedel-Crafts acylation of salicylaldehyde (16) with bromoacetyl bromide in the presence of aluminum chloride gave the acetophenone 17. Alkylation of amine 18 with bromoacetyl 17 in refluxing acetonitrile gave the ketone 19. Reduction of 19 with sodium borohydride in methanol followed by catalytic hydrogenolysis of the benzyl group over 10% Pd/C gave salmeterol (2). 

Sodium Borohydride. Contact of borohydride solution with solid aluminum chloride can lead to ignition of hydrogen.11... 

Acetic anhydride Aluminum chloride Sodium hydroxide Hydrogen peroxide Sodium borohydride Hydrochloric acid... 

Preparation of the Final Compound 2-Methyl-3-o-Tolyl-6-Sulfamyl-7-Chloro-1,2,3,4-Tetrahydro-4(3H)-Quinazolinone To 4 liters of dry diglyme in a 12-liter 3-necked flask fitted with a stirrer, thermometer and drying tube was added 5.34 g (0.04 mol) of aluminum chloride, while stirring. To the resulting solution was added 43.6 g (0.12 mol) of 2-methyl-3-o-tolyl-6-sulfamyl-7-chloro-4(3H)-quinazoline. A solution of 4.56 g (0.12 mol) of sodium borohydride in 1 liter of dry diglyme was added portionwise over a period of 1 hour while stirring the mixture. The mixture was then heated at 85°C, with stirring, for 1 hour. 

Methansulfonyl chloride Aluminum chloride Isopropylamine Sodium borohydride... 

Aluminum chloride Ethyl glycidate N-Chlorodiisopropylamine Hexamethylphosphoramine Sodium borohydride Dimethylacetamide... 

Sodium hydride Hydrochloric acid Aluminum chloride o-Phosphoric acid Sodium hydroxide Palladium on carbon Sodium borohydride l,3-Dihydro-l-benzyl-2H-benzimidazol-2-one... 

Reduction of 9 with sodium borohydride/aluminum chloride has been reported.13... 

DEHALOGENATION Aluminum chloride-E thane thiol. Sodium sulfide. Zine borohydride. 

Sodium aluminum chloride, 435 Sodium amalgam, 310, 416-417 Sodium amide-Sodium r-butoxide, 417-418 Sodium azide-Triphenylphosphine, 418 Sodium bis(2-methoxyethoxy)aluminum hydride, 166,418-420 Sodium borohydiidc, 323,420-421 Sodium borohydride-Alumina, 421 Sodium borohydride-Bis(2,4-pentane-dionato)copper(ll), 421 Sodium borohydride-Cerium(Ill) chloride,... 

Similar results can be obtained if the borane is substituted for the system Sodium Borohydride/Aluminum Chloride. ... 

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