Tert Butyl alcohol anhydrous

Toluene, dichloromethane, acetic acid, ammonium hydroxide, concentrated H2SO4, 5 N NaOH and 37% HCI were purchased from Mallinckrodt Inc. tetrahydrofuran, tert-butyl alcohol, anhydrous Na2S04, and NaCI were purchased from EM Science potassium tert-butoxide was purchased from Aldrich Chemical Company, Inc. hexanes was purchased from Baxter, and dry O2 was purchased from Air Products. All these reagents were used as received. 

Hg [212], is prepared from tert-butyl hydrogen sulfate and 27% hydrogen peroxide [212] and is commercially available as a 70 or 90% solution containing water and tert-butyl alcohol. Anhydrous rert-butyl hydroperoxide is obtained from the 70% aqueous solution by azeotropic distillation with toluene [213]. Anhydrous, as well as highly concentrated, tert-bvXy hydroperoxide must be handled with utmost care, because it may decompose violently in the presence of strong acids and some transition metals, especially manganese, iron, and cobalt [213, 214],... 

The tert.-butyl alcohol should be dried over quicklime or anhydrous calcium sulphate and distilled. 

Prepare anhydrous tert.-butyl alcohol by refluxing the commercial product with sodium ca. 4 g. per 100 ml.) until the metal is about two-thirds dissolved and then distilling. Free metal should be present during the distillation. 

Potassium er -butoxidc was obtained from Sigma-Aldrich and used as received. Alternatively, equivalent results were obtained using t-BuOK that was prepared from potassium metal and anhydrous tert-butyl alcohol (t-BuOH) followed by removal of excess t-BuOH. In this case, the molecular weight of t-BuOK was calculated based on a 1 1 ratio of t-BuOK to t-BuOH (i.e., 186.34 for C8H1902K). 

All reactants should be pure and anhydrous. The tert.-butyl alcohol should be dried over quicklime and the dimethylani-line redistilled. Reagent grade acetyl chloride should be employed. 

Different stereoselectivities caused by solvent effects are demonstrated in the reduction of dihydroisophorone (3,3,5-trimethylcyclohexanone) with sodium borohydride which gave less stable tranj-3,3,5-trimethylcyclohexanol (with axial hydroxyl) by reduction in anhydrous isopropyl alcohol (55-56%), in anhydrous tert-butyl alcohol (55%), in 65% aqeuous isopropyl alcohol (59.5%), in anhydrous ethanol (67%), and in 71% aqueous methanol (73%) (the balance to 100% being the more stable cis isomer with equatorial hydroxyl) [849]. 

A one-liter flask fltted with a stirrer, reflux condenser and separatory flask is charged with 7.6 g (0.2 mol) of lithium aluminum hydride and 500 ml of anhydrous ether. A solution of 44.4 g (0.6 mol) of anhydrous terr-butyl alcohol in 250 ml of ether is added slowly from the separatory funnel to the stirred contents of the flask. (The hydrogen evolved is vented to a hood.) During the addition of the last third of the alcohol a white precipitate is formed. The solvent is decanted and the flask is evacuated with heating on the steam bath to remove the residual ether and tert-butyl alcohol. The solid residue - lithium tri-/er/-butoxyaluminohydride - is stored in bottles protected from atmospheric moisture. Solutions 0.2 m in reagent are prepared by dissolving the solid in diglyme. 

Alkyl nitrites can also be used in anhydrous media and, for example, 4-hydroxyben-zenediazonium tetrafluoroborate is isolated in 89% yield after diazotization with isopcntyl nitrite, hydrogen fluoride and boron trifluoride in ethanol/diethyl ether.96 Diazotization can also be performed in dichloromethane or ethers (diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane) with terl-butyl nitrite and boron trifluoride-diethyl ether complex which generates nitrosyl fluoride in situ.229 Excess boron trifluoride is used to trap water and tert-butyl alcohol, so that the reaction can be considered as being performed under complete anhydrous conditions. Yields are higher in dichloromethane, but 1,2-dimethoxyethane is preferred for less soluble amines. This procedure has been successfully applied to the synthesis of mono-and difluorobenzo[c]phcnanthrenes.230... 

Free cydohexene from peroxides by treating it with a saturated solution of sodium bisulphite, separate, dry and distil collect the fraction, b.p. 81-83°. Mix 8 2 g. of cydohexene with 55 ml. of the reagent, add a solution of 15 mg. of osmium tetroxide in anhydrous tert.-butyl alcohol and cool the mixture to 0°. Allow to stand overnight, by which time the initial orange colouration will have disappeared. Remove the solvent and unused cydohexene by distillation at atmospheric pressure and fractionate the residue under reduced pressure. Collect the fraction of b.p. 120 140°/15 mm. this solidifies almost immediately. Recrystallise from ethyl acetate The yield of pure cts-1 2-cydohexanediol, m.p. 96°, is 5-0 g. 

In a i-l. round-bottomed flask are placed 12 g. (0.5 gram atom) of magnesium powder, 37 g. (0.5 mole) of tert.-butyl alcohol, and 100 g. of anhydrous ether (Note 1). The flask is fitted with an addition tube, one arm of which bears a reflux condenser, and the other arm a dropping funnel. While the mixture is being shaken by hand, a solution of 55 g. (0.7 mole) of acetyl chloride (Note 2) in 50 g. of anhydrous ether is added dropwise (Note 3). A lively reaction gradually ensues with evolution of hydrogen, mixed with ether vapor and a little hydrogen chloride (Note 4). After all the acetyl chloride has been added, the reaction mixture is allowed to stand in a pan of cold water for one hour (Note 5). After another hour at room temperature the mixture is warmed in a water bath at 40-45° for one-half hour in order to complete the reaction. 

The photocyanation and the photohydrolysis of 4-chloroanisole and 4-fluoroanisole have been studied with time-resolved spectroscopy and by measurement of the photoconductivity in anhydrous and aqueous acetonitrile and tert-butyl alcohol solutions632. The mechanism is depicted in equation 167. The transient species which have been... 

The classical method for making tert-butyl esters involves mineral acid-catalysed addition of the carboxylic acid to isobutene but it is a rather harsh procedure for use in any but the most insensitive of substrates [Scheme 6.33].80-82 Moreover, the method is hazardous because a sealed apparatus is needed to prevent evaporation of the volatile isobutene. A simpler procedure [Scheme 6.34] involves use of tert-butyl alcohol in the presence of a heterogeneous acid catalyst — concentrated sulfuric acid dispersed on powdered anhydrous magnesium sulfate. 3 No interna] pressure is developed during the reaction and the method is successful for various aromatic, aliphatic, olefinic, heteroaromatic, and protected amino acids. Also primary and secondary alcohols can be converted into the corresponding /erf-butyl ethers using essentially the same procedure (with the exception of alcohols particularly prone to carbonium ion formation (e.g. p-... 

The amide group is readily hydrolyzed to acrylic acid, and diis reaction is kinetically faster in base than in acid solutions (5,32,33). However, hydrolysis of N-alkyl derivatives proceeds at slower rates. The presence of an electron-with-drawing group on nitrogen not only facilitates hydrolysis but also affects the polymerization behavior of diese derivatives (34,35). Widi concentrated sulfuric acid, acrylamide forms acrylamide sulfate salt, die intennediate of the former sulfuric acid process for producing acrylamide commercially. Further reaction of the salt widi alcohols produces acrylate esters (5). In strongly alkaline anhydrous solutions a potassium salt can be formed by reaction with potassium / Y-butoxide in tert-butyl alcohol at room temperature (36). 

The following chemicals were purchased from Kanto Chemical Co. Inc. and used as received neopentyl glycol, p-toluenesulfonic acid, sodium, and n-BuLi. N,N,N, N -Tetramethylethylenediamine was purchased from Aldrich Chemical Company, Inc. and distilled before use. 1,3-Dichloroacetone was obtained from Wacker Chemicals East Asia and used as received. Reagent grade benzene, pentane, ether, THE, tert-butyl alcohol, acetonitrile, and toluene were purchased from Wako Chemicals Industries Ltd. Benzene, pentane, and tert-butyl alcohol were distilled from CaH ether and THF from sodium benzophenone ketyl immediately before use acetonitrile successively from PjOj and anhydrous KjCOj and toluene from LiAlH. Potassium tert-butoxide and 2-cyclopenten-1-one were purchased from Tokyo Kasei Kogyo Co. Ltd. the ketone was distilled before use. 

A solution of hydrogen peroxide in fer/-butyl alcohol is prepared by adding 400 mL of pure tert-butyl alcohol (free of isobutylene) to 100 mL of 30% hydrogen peroxide. The solution is treated with small portions of anhydrous sodium sulfate until two layers separate. The alcohol layer is removed and dried with anhydrous sodium sulfate and finally with anhydrous calcium sulfate (Drierite). The solution contains 6.3% of hydrogen peroxide in ferf-butyl alcohol. 

Ferrier and Hatton28 found that the condensation of D-xylose with benzaldehyde in tert-butyl alcohol with only anhydrous sodium sulfate as desiccant affords good yields of two diastereoisomeric 1,2 3,5-di-O-benzylidene-xylofuranoses. The diastereoisomerism is confined to the 1,2-acetal ring. Earlier, standard syntheses had produced only the 1,2-exo isomer. 

Butane, 1,4-diiodo-, 30, 33 1,4-dinitro-, 34, 37 2-Butanone, 3-acetamido-, 33,1 tert-Butyl acetate, 34, 28 n-BuTYLACETYLENE, 30, 15 tert-Butyl alcohol, 30, 19, 20 32, 20 anhydrous, 34, 54, 55 /erZ-Butylbenzene, 32, 91 terl-Butyl o-benzoylbenzoate, 34, 28 n-Butyl bromide, 30, 16 tert-Butyl bromoacetate, 34, 28 sec-Butyl a-bromopropionate, 35, 15... 

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