Di--butyl ether

A small residue of di- -butyl ether, b.p. 142°, remains in the flask. 

Like //-butyUithium, j iZ-butyUithium is infinitely soluble in most hydrocarbons, such as pentane and hexane. Its solutions in hexane are flammable and pyrophoric and therefore should be handled like //-butyUithium (96,100). j iZ-ButyUithium also is very soluble in ethers, but the ether solutions must be kept cold because ether cleavage is more rapid than in the presence of //—butyUithium (122). j iZ-ButyUithium has a t 2 of 2 d at 25°C in di-//-butyl ether and of 1 d at 25°C in di-//-hexyl ether. 

AlkoxyaLkyl hydroperoxides are more commonly called ether hydroperoxides. They form readily by the autoxidation of most ethers containing a-hydrogens, eg, dioxane, tetrahydrofuran, diethyl ether, diisopropyl ether, di- -butyl ether, and diisoamyl ether (10,44). From certain ethers, eg, diethyl ether (in the following, R = H R = 35 — CH2CH2), the initially formed ether hydroperoxide can yield alcohol on standing, or with acid treatment... 

Many organic reagents have been used successfully in Pu separation processes. The reagents include tri- -butyl phosphate (TBP) methyl isobutyl ketone thenoyl ttifluoroacetone (TTA) ethers, eg, diethyl ether, di- -butyl ether, tetraethylene glycol dibutyl ether trdaurylamine (TT,A) trioctylamine (TOA) di- -butyl phosphate (DBP) hexyl-di(2-ethylhexyl) phosphate (HDEHP) and many others. Of these, TBP is by far the most widely used (30,95). 

A. m-Butyl Butyrate from Di- -butyl Ether by Ruthenium Tetroxide... 

In a 200-ml round-bottom flask equipped with a magnetic stirrer and a thermometer is placed a mixture of 50 ml of di- -butyl ether and 25 ml of water. The flask is immersed in an ice bath and the mixture is cooled to 5°. In one portion is added 23.2 g (0.1 moles) of trichloroisocyanuric acid (Chapter 17, Section IV), and stirring in the ice bath is continued for 12 hours. The ice bath is removed and the mixture is stirred at room temperature for an additional 8 hours. The reaction mixture is then filtered to remove solids. The water is separated from the organic layer, which is then washed with two additional portions of water, dried with anhydrous sodium sulfate, filtered, and fractionated as above. 

J. B. Ott, K. N. Marsh, and A. E. Richards, "Excess Enthalpies, Excess Gibbs Free Energies, and Excess Volumes for (di-//-Butyl Ether-)- Benzene) and Excess Gibbs Free Energies and Excess Volumes for (di-n-Butyl Ether + Tetrachloromethane) at 298.15 and 308.15 K", /. Chem. Thermodyn., 13, 447-455 (1981). 

Butoxyethanol Dimethoxyethane Diethyleneglycol Dihydropyran 2-Methoxyethanol Di butyl ether 01 pentyl ether Triethyleneglycol... 

This preparation is an example of the use of di- -butyl ether as a solvent in the Grignard reaction. The advantages are it is comparatively inexpensive, it can be handled without excessive loss due to evaporation, simple distillation gives ah ether free from moisture and alcohol, and the vapour does not form explosive mixtures with air. n-Butyl ether cannot, of course, be employed when the boiling point of the neutral reaction product is close to 140°. 

Problem 14.50 Why is di-/-butyl ether very easily cleaved by HI <4... 

This procedure has been used successfully to convert simple aliphatic ethers into their corresponding iodides. Yields of iodides obtained in the reaction of di- -butyl ether and diisopropyl ether with potassium iodide and 95% orthophosphoric acid were 81 and 90% respectively. Small quantities of the corresponding alcohols were also isolated as products from these reactions. 

Less commonly used solvents include methyl ethyl ketone, b.p. 80° ethylene chloride, b.p. 84° dioxan (diethylene dioxide), b.p. 101° (vapours are toxic) toluene, b.p. 110° pyridine, b.p. 115-5° chlorobenzene, b.p. 132° cellosolve (ethylene glycol monoethvl ether), b.p. 134-5° di- -butyl ether, b.p. 141° s-tetrachloro-... 

Prepare a Grignard reagent from 24-5 g. of magnesium turnings, 179 g. (157 ml.) of n-heptyl bromide (Section 111,37), and 300 ml. of di- -butyl ether (1). Cool the solution to 0° and, with vigorous stirring, add an excess of ethylene oxide. Maintain the temperature at 0° for 1 hour after the ethylene oxide has been introduced, then allow the temperature to rise to 40° and maintain the mixture at this temperature for 1 hour. Finally heat the mixture on a water bath for 2 horns. Decompose the addition product and isolate the alcohol according to the procedure for -hexyl alcohol (Section III,18) the addition of benzene is unnecessary. Collect the n-nonyl alcohol at 95-100°/12 mm. The yield is 95 g. 

Other considerations for the solvent are the solubility of the Grignard reagent and the temperatures required for initiation and adventitious reactions of the Grignard with the solvent (16—19). Based on these three considerations, the best general solvent for the preparation of a Grignard reagent is THF. However, other solvents that are commonly used are diethyl ether, methyl /-butyl ether, di- -butyl ether, glycol diethers, toluene, dioxane (R Mg), and hexane. 

C8H180 di butyl ether 142-96-1 1.288E+10 91.920 18182 C9H20 2,2-dimethyfheptane 1071-26-7 1.388E+10 98.930... 

Problem 14.6 Give the alkene and alcohol needed to prepare the following ethers by alkoxymercuration-demercuration (a) diisopropyl ether, (6) 1-methyl-1-methoxycyclopentane, (c) 1-phenyl-1-ethoxypropane, (d) di-/-butyl ether. ... 

Synonyms Dibutyl ether 1-Butoxybutane, dibutyl oxide, di- -butyl ether, n-dibutyl ether Chemical/Pharmaceutical/Other Class Ether Chemical Formula CgHigO Chemical Structure ... 

Di butyl Ether 22 7 Monsanio 1-ustrei SD.S rnm diam. diso... 

The first fractions consist of a little alcohol, water, and di- -butyl ether (Note 5). The next fraction is diethyl sebacate, b.p. 156-158° at 6 mm. (Note 6). Ethyl hydrogen sebacate is collected at 183-187° at 6 mm. The product melts at 34-36° and weighs 114-124 g. (50-54 per cent of the calculated amount, based on the sebacic acid used). Refracfionation of the fore-run (b.p. i75-i83°/6 mm.) and after-rim (b.p. i87-i95°/6 mm.) gives an additional 24-26 g. of pure monoester. The total yield is 138-150 g. (60-65 per cent of the theoretical amount) (Notes 7 and 8). 

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