Terr-Butanol

Typical procedureA solution of tellurium powder (96 mg, 0.75 mmol) and NaBH (42 mg, 1.12 mmol) in 1.5 mL DMF-terr-butanol (100 1) was heated at 80°C for 30 5 min under argon. After this time the resulting deep purple solution was cooled at room temperature and the substrate (0.5 mmol), pyridine (43 pL, 0.5 mmol) in 2 mL of benzene-DMF (1 3) was added via syringe. The mixture was stirred at room temperature until completion of the starting material (TLC). Then, the reaction flask was opened to air and water was added. After 1 h, the mixture was filtered trough Celite , eluted with EtOAc and washed with brine. Chromatography was allowed to obtain the pure products. 

Poly(4-vinylpyridine) [25232-41-1] M (105.1) . Purified by repeated pptn from solns in EtOH and dioxane, and then EtOH and ethyl acetate. Finally, freeze-dried from terr-butanol. 

Conditions 10 mmol olefin, 16 mmol oxidant, 20 ml terr-butanol, 0.75 ml 20% aqueous tetraethyl ammonium hydroxide and 0.005 mmol OSO4 were stirred for 24 h at 0°C. 

B utanetetraylnaph-thalene, decahydro-, 53, 30 terr-Butanol, with p-toluoyl chloride and butyllithium to give ten-butyl p-toluate, 51, 96... 

Finally it is interesting to note that the tetranuclear complex [Ba4(/U>3-OBu )4(OBu )4(Bu OH)g] has a structure based on the cubane unit Ba4(p-3-OBu )4. Each barium ion is six-coordinated by virtue of terminal bonding to one tert-butoxo ligand and two terr-butanol molecules with intramolecular hydrogen bonding. 

Methyl ethyl ketone-terr.-butanol-methanol-6.5 iV ammonium hydroxide (16 3 1 6)... 

Ninhydrin. Spray with 0.3% soln. of ninhydrin in water satd. terr.-butanol, heat at 100-105° for... 

A mixture of diethyl y-oxopimelate and anisaldehyde stirred 45 min. at room temp, in a soln. of K in terr-butanol under inert anhydrous conditions -> / -p-methoxybenzylidene-y-oxo-cw-carbethoxyhexanoic acid. Y 90%. F. e. s. G. Baga-vant and K. B. V. Swaminathan, Current Sci. 44, 661 (1975). 

Weizmann A process for producing acetone and //-butanol by the fermentation of carbohydrates by bacteria isolated from soil or cereals. Later work has shown that effective bacteria are Clostridium acetobutylicum and Bacillus granulobacter pectinorum. Used in Britain in World War I for the manufacture of acetone, needed for the production of cordite. Subsequently operated by Commercial Solvents Corporation in Terre Haute, IN, and in two plants in Canada. Later abandoned in favor of synthetic processes. Invented by C. Weizmann in the University of Manchester in 1915, based on earlier work at the Pastern Institute by A. Fembach and E. H. Strange (hence the alternative name Fembach-Strange-Weizmann). The money that Weizmann obtained from royalties on this process was used in founding the State of Israel, of which he was the first president. 

The Fajula group also recently studied the alkylation of naphthalene with tert-butanol.57 Over H-beta 2-te/t-butylnaphthalene was obtained as the main product together with relatively small amounts of the di-terr-butylnaphthalenes. Over HY 2,6-and 2,7-di-terf-butylnaphthalene the major products, demonstrating again the more spacious Y-pore system. 

When stirred for a few minutes with equimolar amounts of terr.-butyl hypochlorite in methanol/dichloromethane at 0° and then with aqueous sodium hydrogen carbonate solutions, diorgano tellurium compounds were converted in good yields to diorgano tellurium oxides The /ert.-butanol formed during hydrolysis is easily removed under reduced pressure. 

Note that the primary alkoxides (e.g., ethoxides) of some later 3d metals such as Mn11, Fe11, Co11, and Ni11 do not undergo alcoholysis (7, 19) or transesterification with tert-butanol or butyl acetate, whereas their terr-butoxides M(0-t-Bu)2 are easily converted into ethoxides with ethanol. 

One of the most fascinating stories of the coatings industry involves the production of acetone, butanol, and ethanol by the Weizmann process (11. 12). Because the main objective was to produce acetone for explosives, the butanol piled up until it was found that butyl acetate was an excellent solvent for the new nitrocellulose lacquers. Commercial Solvents Corporation (of Maryland) was formed in 1919 to take over the fermentation plants operating at Terre Haute to make butanol and derivatives. The availability of butyl alcohol and the acetate was of major aid in the success of nitrocellulose lacquers in new automobile paints that permitted a reduction in the time required for painting automobiles from 23 days in 1920 to a matter of about 12 h in 1940 (13). 

The Commercial Solvents Corporation, operating corn fermentation plants at Terre Haute, Indiana, and Peoria, Illinois, for the production of butyl alcohol (butanol) has been wasting to the atmosphere from this operation about... 

Isobutene, from which both MTBE and ETBE are obtained, is the olefm of lowest molecular mass from which an ether with antiknock capacity can be obtained. Currently, attention is being turned to ethers of heavier olefins in the range C5-C7 [15-18, 29, 30]. As well as those mentioned above (TAEE, DIPE and BTBE), these heavier ethers include terr-hexyl ethyl ether (THxEE) and ferf-heptyl ethyl ether (THpEE). TAEE, THxEE and THpEE are all obtained by reaction of the corresponding olefin with ethanol, BTBE by reaction of isobutene with n-butanol and DIPE as a by-product of the production... 

Chandrasekhar. This general methodology involves simply refluxing a solution of the tosylhydrazone 26 and potassium terr-butoxide in rer/-butanol, thus affording the required tert-butyl ether 27 in high yield. 

Here, the reaction between methyl iodide and the anion of 2-methyl-2-propanol (terr-butoxide) to form tm-butyl methyl ether is used to demonstrate the process in which a methyl group has been substituted for the proton originally on the oxygen of 2-methyl-2-propanol (tert-butanol) (Equation 8.21). The example of Equation 8.21 is also used to emphasize that the ether (rm-butyl methyl ether) cannot be prepared from the reaction between methoxide anion and 2-iodo-2-methylpropane (or indeed any 2-halo-2-methylpropane) because elinnnation would intrude (Equation 8.22). 

Aporphines. A mixture of N-carbethoxy-l-(6 -bromo-3, 4 -methylenedioxyben-zylidene)-6,7-methylenedioxy-l,2,3,4-tetrahydroisoquinoline, K-terr-butoxide, tert-butanol, and benzene stirred 21 hrs. under N2 with irradiation by the Corex-filtered light of a Hanovia 450 w. lamp. -> N-carbethoxydehydronorneolitsine. Y 72%. M. P. Cava, P. Stern, and K. Wakisaka, Tetrahedron 29, 2245 (1973) cyclic ketones with K-rerr-butoxide in liq. NH3, cephalotaxinone, cf. M. F. Sem-melhack, R. D. Stauffer, and T. D. Rogerson, Tetrah. Let. 1973, 4519. 

The rapid growth in demand for butanol is illustrated by the rate at which the plant capacity was expanded between 1920 and 1927. The Terre Haute plant had 40 fermentors initially, and it was increased to 52 during 1923. When the plant in Peoria began operation at the end of 1923, it had 32 fermentors (50,000 gal each). A year later, the Peoria plant had 48 fermentors, and toward the end of 1927, the number increased to 96 (50,000 gal each), for a total of 148 fermentors for both plants (Gabriel 1928). By 1927, the two plants together produced more than 100 t of solvents per day (Killeffer 1927). After the expiration of the Weizmann patent in 1936, industrial solvent fermentation was practiced around the world as other companies built plants in the United States, Puerto Rico, the United Kingdom, Japan,... 

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