Tert-Butyl alcohol structure

The total pore volume, Vp = 0.23 cm3 g, calculated from this isotherm is considerably lower than those given by other adsorbates for this material3 (see Table 1) including, as will be shown later, tert-butyl alcohol (Vp(fe/-t-butyl alcohol) = 0.33 cm3 g 1). This confirms that complete surface coverage has not occurred during n-butyl alcohol adsorption and also that steric effects have influenced the structure of the adsorbed layer. 

However, we found that TBSE is a rather stable species, decomposing only upon heating above 373 K. Thus, at 296 K it behaves as a side intermediate species, through which only a small fraction of tert-butyl alcohol molecules dehydrate. The main reaction stream bypasses the TBSE structure, proceeding presumably through the terf-butyl cation ion as the key intermediate (Scheme 4). 

However, depending on the particular structure of both the reactant (i.e., n-, sec-, iso-, or tert-butyl alcohol) and catalyst (i.e., amorphous AAS or crystalline HZSM-5, of specific crystallite size), the observed reaction rates and selectivity... 

Here I would like to mention attempts of synthesizing carbynoid structures by Kijima et al. [6,9] using electrochemical approach. Cathodic electrolysis of a solution of poly(vinylidene fluoride) (PVDF) in DMF containing tetrabutylammonium perchlorate, and tert-butyl alcohol as a mediator was found to produce -doped conjugated polymers consisting of 76% of poly(fluoro-acetylene) and 24% of carbynoid moieties [6] (Scheme 12.7) ... 

Because the compound reacts with Na, it must be an alcohol. Furthermore, because the compound does not react with a strong oxidizing agent, it must be a tertiary (3°) alcohol. Therefore, the structure of C4H10O is tert-butyl alcohol ... 

Mukai and co-workers [105] used Keggin-type heteropolyacids immobilized in the network structure of resorcinol-formaldehyde carbon gels as catalysts for the synthesis of methyl tert-butyl ether from methyl alcohol and tert-butyl alcohol. Large amounts of 12-tungstophosphoric and 12-molybdophosphoric acids were immobilized into the support by two methods, pore shrinkage and the ship-in-the-bottle method, which are essentially impregnation methods. The authors reported that these catalysts showed activity in the reaction studied and could be of practical utility as solid acid catalysts in various reactions. 

Figure 16.1. Molecular structure of some amphiphilic solutes, (a) Dimethyl sulphoxide (DMSO), (b) methanol (MeOH), (c) ethanol (EtOH), (d) tert-butyl alcohol (TEA), (e) acetone. For all these solutes the partial charges are indicated on the corresponding atoms according to the GROMOS-96 force field, (f) Molecular structure of 1,4-dioxane. For 1,4-dioxane the partial charges are indicated on the respective atoms according to / Am. Chem. Soc., 127 (2005), 11019-11028.

C provides direct support for the dictum that tertiary carbonium ions are more stable than secondary, which are more stable than primary. Primary and secondary alcohols are protonated under these conditions, and the protonated alcohols are the species observed (entry 1), while tert-butyl alcohol yields ter/-butyl cation at rates too fast to measure. The rates of cleavage of protonated primary and secondary alcohols depend on their structure. Protonated sec-butanol cleaves with rearrangement to (CH3)3C and water slowly at -60°C, protonated isobutanol cleaves with rearrangement at —30°C, and protonated n-butanol at 0°C. It is typical of reactions in superacid media that the most stable ion of a particular class is observed because, under conditions in which the ions are long-lived, intramolecular hydride shifts and rearrangement processes occur that lead ultimately to the most thermodynamically... 

Lei Z, Yang Y, Li Q, Chen B. Catalytic distillation for the synthesis of tert-butyl alcohol with structured catalytic packing. Catal. Today 2009 147S S352-S356. 

As the product Al(OPr )(OBu )2 is found to be dimeric it was suggested that aluminium atoms on being surrounded by bulky isopropoxy and tert-butoxy groups in a structure of the type (2-1), are shielded so effectively that the lone pair orbital of the oxygen atom of another tert-butyl alcohol molecule cannot approach sufficiently close to the d orbitals of aluminium for the interaction to be initiated. A finer difference in susceptibilities to steric factors was further demonstrated by the fact that with aluminium ethoxide, some further (albeit extremely slow) replacement was possible. 

Write structural formulas for all the products that would be obtained when each of the following alkyl halides is heated with potassium tert-butoxide in tert-butyl alcohol. When more than one product results, you should indicate which would be the major product and which would be the minor produces). You may neglect cis-trans isomerism of the products when answering this question. 

See for example Harris, K. R. Newitt, P. J. Diffusion and structure in water-alcohol mixtures water-l-tert-butyl alcohol, J. Phys. Chem. 1999, 103, 6508-6513. 

K. Yoshida, T. Yamaguchi, A. Kovalenko and F. Hirata. Structure of tert-butyl alcohol-water mixtures studied by the RISM theory. J. Phys. Ghem. B 106, 2002, 5042-5049. 

The lipase-catalyzed resolutions usually are performed with racemic secondary alcohols in the presence of an acyl donor in hydrophobic organic solvents such as toluene and tert-butyl methyl ether (Scheme 1.3). In case the enzyme is highly enantioselective E = 200 or greater), the resolution reaction in general is stopped at nearly 50% conversion to obtain both unreacted enantiomers and acylated enantiomers in enantiomerically enriched forms. With a moderately enantioselective enzyme E = 20-50), the reaction carries to well over 50% conversion to get unreacted enantiomer of high optical purity at the cost of acylated enantiomer of lower optical purity. The enantioselectivity of lipase is largely dependent on the structure of substrate as formulated by Kazlauskas [6] most lipases show... 

From the decomposition mechanism and the products formed it can be deduced that DCP primarily generates cumyloxy radicals, which further decompose into highly reactive methyl radicals and acetophenone, having a typical sweet smell. Similarly, tert-butyl cumyl peroxide (TBCP) forms large quantities of acetophenone, as this compound still half-resembles DCP. From the decomposition products of l-(2-6 rt-butylperoxyisopropyl)-3-isopropenyl benzene ( ), it can be deduced that the amount of aromatic alcohol and aromatic ketone are below the detection limit (<0.01 mol/mol decomposed peroxide) furthermore no traces of other decomposition products could be identified. This implies that most likely the initially formed aromatic decomposition products reacted with the substrate by the formation of adducts. In addition, unlike DCP, there is no possibility of TBIB (because of its chemical structure) forming acetophenone. As DTBT contains the same basic tert-butyl peroxide unit as TBIB, it may be anticipated that their primary decomposition products will be similar. This also explains why the decomposition products obtained from the multifunctional peroxides do not provide an unpleasant smell, unlike DCP [37, 38]. 

Here we report the synthesis and catalytic application of a new porous clay heterostructure material derived from synthetic saponite as the layered host. Saponite is a tetrahedrally charged smectite clay wherein the aluminum substitutes for silicon in the tetrahedral sheet of the 2 1 layer lattice structure. In alumina - pillared form saponite is an effective solid acid catalyst [8-10], but its catalytic utility is limited in part by a pore structure in the micropore domain. The PCH form of saponite should be much more accessible for large molecule catalysis. Accordingly, Friedel-Crafts alkylation of bulky 2, 4-di-tert-butylphenol (DBP) (molecular size (A) 9.5x6.1x4.4) with cinnamyl alcohol to produce 6,8-di-tert-butyl-2, 3-dihydro[4H] benzopyran (molecular size (A) 13.5x7.9x 4.9) was used as a probe reaction for SAP-PCH. This large substrate reaction also was selected in part because only mesoporous molecular sieves are known to provide the accessible acid sites for catalysis [11]. Conventional zeolites and pillared clays are poor catalysts for this reaction because the reagents cannot readily access the small micropores. 

---