Tert-amyl acetate

Successful results have been obtained (Renfrow and Chaney, 1946) with ethyl formate methyl, ethyl, n-propyl, iso-propyl, n-butyl, i o-butyl, sec.-butyl and iso-amyl acetates ethylenegl3rcol diacetate ethyl monochloro- and trichloro-scetates methyl, n-propyl, n-octyl and n-dodecyl propionates ethyl butyrate n-butyl and n-amyl valerates ethyl laurate ethyl lactate ethyl acetoacetate diethyl carbonate dimethyl and diethyl oxalates diethyl malonate diethyi adipate di-n-butyl tartrate ethyl phenylacetate methyl and ethyl benzoates methyl and ethyl salicylates diethyl and di-n-butyl phthalates. The method fails for vinyl acetate, tert.-butyl acetate, n-octadecyl propionate, ethyl and n-butyl stearate, phenyl, benzyl- and g aicol-acetate, methyl and ethyl cinnamate, diethyl sulphate and ethyl p-aminobenzoate. 

Another highly active non-pyrophoric nickel catalyst is prepared by reduction of nickel acetate in tetrahydrofuran by sodium hydride at 45° in the presence of tert-amyl alcohol (which acts as an activator). Such catalysts, referred to as Nic catalysts, compare with P nickel boride and are suitable for hydrogenations at room temperature and atmospheric pressure, and for partial reduction of acetylenes to civ-alkenes [49]. 

A vial containing ( )-4-phenyl-3-butyn-2-ol (73.0 mg, 0.500 mmol) and catalyst 16 (3.3 mg, 0.005 mmol) in tert-amyl alcohol (1.0 mL) was capped with a septum and sonicated to help dissolve the catalyst. The resulting purple solution was cooled to 0 °C, and Ac O (35.4 pL, 0.375 mmol) was added by syringe. After 49 h, the reaction mixture was quenched by the addition of a large excess of MeOH. After concentration in vacuo, the residue was purified by FC on sihca gel (EtOAc/hexanes, 1/9 — 1/1 then EtOAc/hexanes/ EtjN, 9/9/2) to afford the (l )-acetate (68.6% ee by chiral-GC) and the (5)-alcohol (96.0%ee by chiral-GC on the acetate obtained following esterification). The calculated selectivity value at 58.3% conversion was s = 20.2. 

Ethyl acetate. n-Propyl acetate iso-Propyl acetate n-Butyl acetate iso-Butyl acetate sec.-Butyl acetate tert.-Butyl acetate n-Amyl acetate iso-Amyl acetate n-Hexyl acetate cycZoPentyl acetate. cycioHexyl acetate. ... 

Ammonolysis, 401 Ampoules, glass. 205 n-Amylamine, 413, 417 n-Amyl acetate, 383 -Amyl alcohol, 247, 249 n-Amylbenzene, 511, 517 n-Amyl borate, 305 n-Amyl bromide, 279 tao-Amyl bromide, 279 n-Amyl chloride, 273 tao-Amyl chloride, 273 tert.-Amyl chloride, 275 n-Amyl cyanide, 407, 408 Amylene, 239 n-Amyl fluoride, 272, 289 n-Amyl iodide, 288 n-Amyl nitrite, 302, 306... 

Jeong, Kim et al. reported use of the chiral DMAP derivative 22e, which was synthesized from 3-amino-DMAP, Kemp s triacid, and N-acetyl-2,2 -diamino-l,l -binaphthyl [26], As summarized in Scheme 12.11, selectivity factors up to 21 were observed with 1 mol% modular catalyst 22e in the kinetic resolution of a variety of secondary alcohols with acetic anhydride in tert-amyl alcohol as solvent, conditions first described by Fu et al. [20]. 

The ketone group in trialkyl phosphonoglyoxylates is highly electrophilic, being quantitatively converted to the hydrate by addition of one equivalent of water, and there is no evidence for rapid exchange on the NMR time scale. The hemi-acetal from methanol also forms quantitatively and showed no sign of conversion to hydrate when kept 48 h in water at room temperature. However, one equivalent of a more hindered tert-amyl) alcohol gave only about 5% hemiac-etal. 

When cross-linked crystals of thermolysin were applied in peptide synthesis in ethyl acetate, they were stable for several hundred hours at amazingly low enzyme consiunption, whereas a soluble enzyme preparation became inactive within a short period of time. Again it is worthwhile to consider the quality of the soluble enzyme preparation. When soluble thermolysin was stored in mixed aqueous-organic solutions, it lost about 50% of its activity within the first day of incubation only to be then quite stable for the next 15 days. It is possible that the initial inactivation was caused by an unstable fraction of thermolysin and that crystals of thermolysin no longer contained this unstable fraction [118]. Productivity comparable to that of crystals was achieved with thermolysin adsorbed on Amberlite XAD-7 resin which was employed in continuous plug flow reactors with tert-amyl alcohol as solvent [119]. 

For the other fuel oxygenates detailed studies on the reaction pathways are not as abundantly available in literature. However, the similarity in chemical structure implies similar reaction by-products. In the case of TAME, tert-amyl formate and tert-amyl alcohol were observed instead of fBF and fBA, and their subsequent degradation products however, acetone and methyl acetate were observed as well [117]. The attack on the methoxy group was observed to be the major pathway, corresponding to the MTBE ehmination. During the elimination of ETBE the same reaction by-products were observed as with MTBE, with the exception of fert-butyl acetate which was formed instead of fBF [30]. 

A mixture of tert-amyl alcohol (2.2 ml, 1.77 g, 20 mmol) and anhydrous THF (10 ml) was added dropwise to a suspension of degreased sodium hydride (1.44 g, 60 mmol) and dried nickel(ll) acetate (1.77 g, 10 mmol) in refluxing THF (20 ml) containing 2,2 -bipyridine (5, 3.12 g, 20 mmol). The reaction mixture was refluxed for 2 h to obtain a solution of NiCRA-bpy reagent. Then, the solution of 4-chloroanisole (76,... 

Aminothiarole n-Amy] acetate iso-Amvl acetate n-Atnyl alcohol 7-Amyl alcohol Inactive Amyl alcohol leo-Amy] alcohol sec-Amyl alcohol tert-Amyl alcohol n-Amylamine iso-Amylamine n-Amylbenzene iso-Amyl bromide iso-Amyl-n-butyrate iso-Amyl chlcu ide iso-Amyl cyanide iso-AmvIene Amylene bromide Aroylene chloride iso-Amyl ether iso-Amyl formate Amylidene chloride... 

Trivial name Acetaldehyde Acetamide Acetic acid Acetic anhydride Acetoacetic acid Acetone Acetonitrile Acetophenone Acetyl chloride Acetylene Acrolein Acrylamide Acrylic acid Acrylonitrile Adipic acid Amyl acetate Amyl alcohol tert-Amy alcohol Aniline Azelaic acid Benzoic acid Benzoyl peroxide Benzyl alcohol Bisphenol A... 

Yu and coworkers [20] reported that the ortho alkenylation of phenylacetic acids proceeds efHciently in the presence of a Pd(OAc)2/benzoquinone catalyst system under basic conditions with KHCO3 in tert-amyl alcohol under Oj atmosphere to afford (2-alkenylphenyl)acetic acids (Scheme 18.20). In contrast to the reaction of benzoic adds (Scheme 18.11), the nudeophilic cychzation of... 

Kinetic analyses were performed for the inactivation of the immobilized enzyme onto Amberlite XAD-7 in ethyl acetate and tert-amyl alcohol at 70°C, varying the water content in the bulk organic solvent phase. The results are shown in Table 2 [59]. The kinetic parameter 2 reflects the effect of the conformational change of enzyme, that is, a change from the active to inactive... 

With an increase in the water content in the bulk organic solvent, the A 2 [Eo] value appreciably increased, as shown in Table 2. The increased A 2 [Eo] values with an increase in the water content in the bulk organic solvent might be ascribed to the increased fraction of the aqueous phase in which the enzyme aggregates exist, which promoted autolysis. To test this speculation, the relative remaining activity after 5-h incubation at 70°C at 4% water content in the bulk organic solvent was plotted against the water content inside the support, for enzyme immobilized onto various supports in addition to Amberlite XAD-7 in ethyl acetate and in tert-amyl alcohol (Fig. 12) [59]. The values of... 

The petroleum industry seldom encounters azeotropes because the hydrocarbon components have similar molecular stmctures. The chemical industry, on the other hand, frequently deals with components of different types, which often produce azeotropes. Common examples are the production of methyl acetate, tetrahydrofuran, tert-amyl methyl ether, isopropanol, vinyl acetate, and many others. 

FDNP- and DNP-pyridoxamine-P can be chromatographed on a cellulose thin layer developed in water/acetone/tert-amyl alcohol/acetic acid (20/35/40/5) their respective Rf values are 0.56-0.61 and 0.50-... 

Isobutyl nitrite Butyl alcohol scc-Butyl alcohol t r -Butyl alcohol Ethyl ether Isobutyl alcohol Ethyl sulfide Pyridine Isovaleraldehyde 3-Methyl 2-butanone Isobutyl formate Isopropyl acetate Methyl isobutyrate Isoamyl nitrite tert-Amyl alcohol Isoamyl alcohol... 

Propanol-pyridine-acetic acid-acetonitrile-water (45 30 9 40 36) tert.-Amyl alcohol-acetone-water (2 1 2) Ethyl acetate-acetic acid-water (3 1 1)... 

Also obtained by reaction of vinyl acetate on resacetophenone mediated by Pseudomonas cepacia lipase in cyclohexane/tert-amyl alcohol at 40° (55-65%) [2898],... 

Also obtained by treatment of respropiophenone in a 9 1 (vol/vol) mixture of cyclohexane/tert-amyl alcohol with vinyl acetate (5 equiv) in the presence of Pseudomonas cepacia lipase adsorbed on Celite for 24 h at 40° (20%) [6761]. 

The direct cyclization of the 3,5-diketone (205) with sodium tert-amyl-oxide (yield about 81%) or by successive treatment with pyrrolidine and aqueous acetic acid (yield about 87%) enables the -diene (209) to be... 

Unsaturated Hydrocarbons. Olefins from ethylene through octene have been converted into esters via acid-catalyzed nucleophilic addition. With ethylene and propjiene, only a single ester is produced using acetic acid, ethyl acetate and isopropyl acetate, respectively. With the butylenes, two products are possible j -butyl esters result from 1- and 2-butylenes, whereas tert-huty esters are obtained from isobutjiene. The C5 olefins give rise to three j iC-amyl esters and one /-amyl ester. As the carbon chain is lengthened, the reactivity of the olefin with organic acids increases. 

---