Tert. Butanol

Most -butanol is now obtained as a co-product of Arco s propylene oxide manufacture (section 12.8.2). In addition to minor speciality uses, some is used directly in gasoline, but most is dehydrated to isobutene for conversion into MTBE (methyl -butyl ether), a preferred octane improver in reformulated (lead-free) gasoline. 

The demand for MTBE has now far outstripped this source of isobutene, and most is obtained by contacting mixed C4 streams with methanol and an acidic ion-exchange resin  

The EPA proposal on use of renewable resources, referred to in section 12.7.1, could mean some displacement of MTBE by ethanol addition or substitution of ethanol for methanol in the above reaction, to give ETBE (ethyl r-butyl ether) in future. 

Maleic anhydride (MA) is important in the production of unsaturated polyesters, used mainly for glass-fibre resin products. The long-established oxidation of benzene over vanadia catalysts at 40(M50°C is very wasteful, with only 40% of the carbon incorporated into the product at a typical selectivity of 60% of theory. Mitsubishi in Japan (and a small European plant) oxidize a stream rich in n-butenes, but with a selectivity of only 45%. 

However, a number of companies in the U.S.A. developed catalysts to give better yields from -butane (including BP Sohio in fluid-bed reactors), and this feedstock is now used for all U.S. production (190 kt per annum) and new plants worldwide. 

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TERT-BUTANOL 293-426 -3.051IE402 -4 6564E 02 -2 0836E-01 6.276SE 01 9.3294E-05... 

Hydroxypyridine (86, R = H) and its derivatives also belong to the class of heterocyclic enols. In benzene and dioxane, 3-hydroxy-pyridine occurs as the neutral molecule (and not as a betaine).Its reaction with diazomethane, in heterogeneous media, gives a mixture of 3-methoxypyridine (86, R = Me) (10%) and l-methyl-3-hydroxy-pyridinium betaine (87) (30%If tert-butanol is used as a... 

The second major discovery regarding the use of MTO as an epoxidation catalyst came in 1996, when Sharpless and coworkers reported on the use of substoichio-metric amounts of pyridine as a co-catalyst in the system [103]. A change of solvent from tert-butanol to dichloromethane and the introduction of 12 mol% of pyridine even allowed the synthesis of very sensitive epoxides with aqueous hydrogen peroxide as the terminal oxidant. A significant rate acceleration was also observed for the epoxidation reaction performed in the presence of pyridine. This discovery was the first example of an efficient MTO-based system for epoxidation under neutral to basic conditions. Under these conditions the detrimental acid-induced decomposition of the epoxide is effectively avoided. With this novel system, a variety of... 

The common names of 2-methyl-2-propanol are tertiary-butanol and tertiary-butyl alcohol (commonly shortened to tert-butanol and tert-butyl alcohol or even t-butanol and t-butyl alcohol). 

Lithium-tri-tert.-butyloxy-hydrido-aluminat5 6 Zu einer Losung von 38 g (1 Mol) Lithiumalanat in 2,5 / abs. Diathylather werden unter Riihren und unter Stickstoff Iangsam 231 g (3,15 Mol) tert.-Butanol in 1 / abs. Diathylather getropft. Unter Wasserstoff-Entwicklung scheidet sich gegen Ende der Reaktion ein voluminoser Niederschlag ab. Man dekantiert, wascht mit Diathylather und trocknet Ausbeute 254 g (100% d.Th.). 

Aus Flavylium-Salzen werden mit Lithiumalanat hauptsachlich 4H-Flavene gebildet1. Natriumboranat ergibt in niedrigeren Alkoholen Dimerisierungsprodukte, in Acetonitril oder tert.-Butanol liefert es ebenfalls die 4H-Flavene z. B.2 ... 

Die Zersetzung des Hydrid-Oberschusses geschieht mit tert.-Butanol, das die Verschie-bung des Gleichgewichts nicht stort. 

Dimethyl-oxiran wirddagegenunter ahnlichenBedingungen in 55%iger Ausbeute zu einem Alkohol-Gemisch reduziert, das 5—7% tert.-Butanol und 93—95% 2-Methyl-propanol enthalt7 ... 

Our own earlier work on the chlorination of toluene had been subject to similar constraints. In this case, chlorination with ferf-butyl hypochlorite had proved to be advantageous. In the presence of silica gel as catalyst the yield of chlorotoluenes was quantitative but the regioselectivity was more or less statistical (ref. 8). However, the use of proton-exchanged zeolite X allowed the production of chlorotoluenes with a para-selectivity of more than 90 % (Fig. 4) (ref. 9). No HCl is generated in this process since the by-product is tert-butanol, and there is no inhibition of the catalyst. Indeed, the catalyst can be reused if necessary. 

Because trimethylsilanol 4 is more acidic than methanol or tert-butanol, tri-methylsilanol 4 and hexamethyldisiloxane 7 react rapidly with 12 M NaOH, KOH, or LiOH to give colorless crystalline precipitates of sodium trimethylsilanolate 96... 

Finally, reaction of primary, secondary, or tertiary alcohols 11 with Me3SiCl 14 in the presence of equivalent amounts of DMSO leads via 789 and 790 to the chloro compounds 791 [13]. n-Pentanol, benzyl alcohol, yS-phenylefhanol or tert-butanol are readily converted, after 10 min reaction time, into their chloro compounds, in 89-95% yield, yet cyclohexanol affords after reflux for 4 h cyclohexyl chloride 784 in only 6% yield [13] (Scheme 6.5). 1,4-Butanediol is cyclized to tetrahydrofuran (THF) [13a], whereas other primary alcohols are converted in 90-95% yield into formaldehyde acetals on heating with TCS 14 and DMSO in benzene [13b] (cf also the preparation of formaldehyde di(n-butyl)acetal 1280 in Section 8.2.1). 

On the other hand, in case of the direct (3-glucosidation using 4-equivalents of 4-hydroxyphenylethyl alcohol and cinnamyl alcohol congeners in 90% tert-butanol/HjO solution (method II), chemical yields of (3-D-glucopyranosides were not always satisfactory and should be improved (Table 4, entries 5-11). 

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