Ferf-Butanol

The danger of explosions dining oxidation of the nitroso compound to perfluoro-ferf-butanol with nitrogen oxides and subsequent hydrolysis, was reduced by working in a flow system at 160-210°C with 8-10% of nitrogen oxides in air, and using cone, sulfuric acid for hydrolysis. 

The pH optimum of HRP is around pH 5. Therefore, this would be the pH of choice. Unfortunately this is not the optimal pH for the light-generating reaction (the general base-catalyzed reaction of acridinium ester with hydrogen peroxide). An acridan ester like GZ-11 with a leaving group of low pKa (perfluoro-ferf-butanol has a pKa below 6) is clearly advantageous. 

Izumi and Urabe [105] found first that POM compounds could be entrapped strongly on active carbons. The supported POMs catalyzed etherization of ferf-butanol and n-butanol, esterification of acetic acid with ethanol, alkylation of benzene, and dehydration of 2-propanol [105], In 1991, Neumann and Levin [108] reported the oxidation of benzylic alcohols and amines catalyzed by the neutral salt of Na5[PV2Mo10O40] impregnated on active carbon. Benzyl alcohols were oxidized efficiently to the corresponding benzaldehydes without overoxidation ... 

Butanol, see sec-Butyl alcohol n-Butanol, see 1-Butanol n-Butan-l-ol, see 1-Butanol s-Butanol, see sec-Butyl alcohol sec-Butanol, see sec-Butyl alcohol f-Butanol, see ferf-Butyl alcohol ferf-Butanol, see ferf-Butyl alcohol Butan-l-ol, see 1-Butanol Butan-2-ol, see sec-Butyl alcohol... 

Solvent was anhydrous THF. 100% excess of the salt of the psuedo acid used (no sodium acetate). Solvent was ferf-butanol. Equivalent amounts of reactants and sodium acetate used unless otherwise stated. Reactions conducted in aqueous methanol unless otherwise stated. 

Alternatively, microwave heating to 120°C was used for the synthesis of Boc-protected aniline because of the lower nucleophilicity of ferf-butanol. 

Irradiation of y-ketoamide 41 affords stereoisomeric lactams 42a and b via hydride abstraction from e-position to the keto group (88H(27)133, 98T2529). The observed stereoselectivity in dichloromethane (88% 42a) is significantly higher than that obtained in ferf-butanol. An additional stereocenter in j5-position to the keto group of amide 41 inverts the dia-stereoselectivity (98MI1). 

N-Heterocyclic carbenes are an example of a family of nucleophilic catalysts [84-87]. For instance, the polymerization of p-butyrolactone was catalyzed by l,3,4-triphenyl-4,5-dihydro-l//,l,2-triazol-5-ylidene in the presence of methanol as an initiator [86]. This reaction was carried out in toluene at 80 °C. Nevertheless, an undesired elimination (Fig. 4) reaction was observed and control of the polymerization was lost. This issue was overcome by using ferf-butanol as a co-solvent, which reacts reversibly with the free carbene to form a new adduct. Owing to the decrease in the concentration of the free carbene, the elimination is disfavored and the polymerization is then under control provided that a degree of polymerization below 200 is targeted. As a rule, the reactivity of N-heterocyclic carbenes depends on their substituents. Hindered N-heterocyclic carbenes turned out to be not nucleophilic enough for the ROP of sCL. Recently, it was shown that unencumbered N-heterocyclic carbenes were more efficient catalysts [87]. 

The first variant works with isobutane as the hydroperoxide precursor, which is oxidized to TBHP by molecular oxygen. During the epoxidation of propene, TBHP is transformed to ferf-butanol, which is converted to methyl ferf-butyl ether. The second procedure employs ethylbenzene, which is oxidized by molecular oxygen to phenyl ethyl hydroperoxide, which transfers an oxygen to propene and so is reduced to phenylethanol. This by-product of the process is converted to styrene, a versatile bulk chemical. 

DHQD)2PHAL] as chiral ligand (Scheme 178) . In order to obtain maximum enan-tioselectivity, the solvent was changed from acetone to ferf-butanol (in some cases a mixture of acetone/H20 proved to be the best solvent), the olefin was added slowly and an excess of ligand relative to osmium (Osdigand 1 3) was used. Various phenyl-substituted internal and terminal olefins have been oxidized to the corresponding diols in... 

Confirmation was provided by the observation that the species produced by the photolysis of two different carbene sources (88 and 89) in acetonitrile and by photolysis of the azirine 92 all had the same strong absorption band at 390 nm and all reacted with acrylonitrile at the same rate (fc=4.6 x 10 Af s" ). Rate constants were also measured for its reaction with a range of substituted alkenes, methanol and ferf-butanol. Laser flash photolysis work on the photolysis of 9-diazothioxan-threne in acetonitrile also produced a new band attributed the nitrile ylide 87 (47). The first alkyl-substituted example, acetonitrilio methylide (95), was produced in a similar way by the photolysis of diazomethane or diazirine in acetonitrile (20,21). This species showed a strong absorption at 280 nm and was trapped with a variety of electron-deficient olefinic and acetylenic dipolarophiles to give the expected cycloadducts (e.g., 96 and 97) in high yields. When diazomethane was used as the precursor, the reaction was carried out at —40 °C to minimize the rate of its cycloaddition to the dipolarophile. In the reactions with unsymmetrical dipolarophiles such as acrylonitrile, methyl acrylate, or methyl propiolate, the ratio of regioisomers was found to be 1 1. 

The alternative strategy for heterogenization has been pursued by Blechert and co-workers, for a polymer-supported olefin metathesis catalyst. A polymer-anchored carbene precursor was prepared by coupling an alkoxide to a cross-linked polystyrene Merrifield-type resin. Subsequently, the desired polymer-bound carbene complex was formed by thermolytically induced elimination of ferf-butanol while heating the precursor resin in the presence of the desired transition metal fragment (Scheme 8.30). 

Acid-treated clays Alcylation reactions (e.g. of benzene with benzyl chloride) Dimerization reactions (e.g. of a-methylstyrene) Etherification reactions (e.g. of ferf-butanol with methanol) Condensation reactions (e.g. of cyclohexanone) Separation of close boiling aromatic amines Separation of isomers of xylene... 

The reaction is usually run in aqueous acetone in either one- or two-phase systems, but substrate solubility may require the use of other solvents. Aqueous ferf-butanol, tetrahydrofuran, and mixtures of these solvents have also been used successfully. 

Beltran o,. cyuv distilled water with/without scavengers OH, UV HC03-, C032, ferf-butanol B hydroxyl radical initiating term prediction was only possible with B included... 

A series of rapid microwave-mediated ester syntheses using Mo(CO)6 as the carbon monoxide source were published in 200374. In this paper, a range of valuable ester-protected acids (butyl-, benzyl- and trimethylsilylethyl esters) were smoothly produced both in solution (Scheme 2.32) and on solid phase (TentaGel S RAM-resin, Scheme 2.33) after 15-20 min of single-mode microwave irradiation. The use of DMAP as a nucleophilic additive increased the product yields slightly. Unfortunately, the sterically hindered ferf-butanol furnished little or no product formation at all. 

A silafulvene (79) was also formed when the 2-diazo-l,2-dihydrosilin 77 was decomposed under copper catalysis (equation 17)49,50. In the presence of ferf-butanol, 79 was trapped as the (terf-butoxy)silane 81. When 77 was decomposed in the presence of ben-zophenone or benzaldehyde, fulvenes 80 were obtained in another reaction typical for silenes. 

The photochemical decomposition of the same diazo compound in ferf-butanol/benzene generated five products, in which either one or two alcohol molecules are incorporated and which are obviously derived from diazosilene and bissilene intermediates. 

The synthesis of (Ph2Si0)8[A10(0H)]4 is performed by reaction of diphenyl-silandiol Ph2Si(OH)2 in diethyl ether with fert-butoxy alane (tBuO-AlH2)2.73 As may be seen from Eq. (1) the products of this reaction are, besides (Ph2SiO)8 [A10(0H)]4, dihydrogen and ferf-butanol.70... 

See Hydrogen peroxide ferf-Butanol, Sulfuric acid... 

Large-scale preparation by addition of ferf-butanol to chromium trioxide in a full unstirred flask with poor cooling detonated owing to local overheating. Effective cooling and stirring are essential [1]. It may safely be prepared by addition of a 40% aqueous solution of chromium trioxide to the alcohol [2]. 

DMF, the oxide must be finely divided, as lumps cause violent local reaction on addition to the solution [2]. Use of methanol to reduce the Cr(VI) oxide to a Cr(III) derivative led to an explosion and fire [3]. The ignitability of the butanols decreases from n- through sec- to ferf-butanol [4]. 

See ferf-Butanol, etc. 2-Phenyl-1,1-dimethylethanol 3,5-Dimethyl-3-hexanol, all below... 

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