Octanol reaction

Figure 13.3 Competitive dehydrogenation of cyclooctanol and 1-octanol. Reaction conditions 1-octanol (0.5 mmol), cyclooctanol (0.5 mmol), styrene (1 mmol), 8% Cu/Al203 (100mg), toluene (8 ml), 363 K, N2 atmosphere.

The etherification of glycols and fatty alcohols is an important reaction [73,113], The relatively large molecular size of the reactants and products makes this reaction more readily manageable over catalytic materials within the mesoporous and/or macroporous range, in comparison with a more traditional acid-based catalyst. In the presence of AlTf-UVM-7, characterized by a low amount of aluminum in the structure network and a high density of Al(OTf)2 acid sites, the condensation of 1-octanol reactions (Equation (8.49)) occurred with high conversions of 1-octanol. 

The hydrophobic constant r is a measure of the contribution of a substituent X to the lipophilidty of compound R-X compared with R-H. The constant representing the solvent/solvent system, analogously to Hammett s p constant for the reaction type, was arbitrarily set to 1 for octanol/water and thus does not appear in Eq. (7). The lipophilidty constant ti allows the estimation of log P values for congeneric series of compounds with various substituents (see Eq. (8)). 

The formation of 2.6-octadienol (27) by the reaction of 1,3-butadiene with water has attracted attention as a novel method for the commercial production of n-octanol, which has a considerable market. However, the reaction of water under the usual conditions is very sluggish. The addition of CO2 facilitates the telomerizdtion of water and 2,6-octadienol (27) is obtained as a major pro-duct[31]. In the absence of CO2, only 1,3,7-octatriene (7) is formed. Probably octadienyl carbonate is formed, which is easily hydrolyzed to give 27. A com-... 

Which of these two opposite stereochemical possibilities operates was determined in experiments with optically active alkyl halides In one such experiment Hughes and Ingold determined that the reaction of 2 bromooctane with hydroxide ion gave 2 octanol having a configuration opposite that of the starting alkyl halide... 

The same cannot be said about reactions with alkyl halides as substrates The conver Sion of optically active 2 octanol to the corresponding halide does involve a bond to the chirality center and so the optical purity and absolute configuration of the alkyl halide need to be independently established... 

Trioctylamine has been prepared, in a continuous process, using 5,200 kg of -octanol, 100 kg of copper formate catalyst, 500 kg of -octylamine, 10 kg of calcium hydroxide, and 240 kg of ammonia (58). Ammonia was added over a 10-h period while 10 m of hydrogen/h was passed through the reactor at a reaction temperature of 180—200°C. The final product was composed of 94% trioctylamine, 2% dioctylamine, 1% octylamine, and 0.5% -octanol. A... 

Alkali Fusion. Tha alkaU fusion of castor oil using sodium or potassium hydroxide in the presence of catalysts to spHt the ricinoleate molecule, results in two different products depending on reaction conditions (37,38). At lower (180—200°C) reaction temperatures using one mole of alkah, methylhexyl ketone and 10-hydroxydecanoic acid are prepared. The 10-hydroxydecanoic acid is formed in good yield when either castor oil or methyl ricinoleate [141-24-2] is fused in the presence of a high boiling unhindered primary or secondary alcohol such as 1- or 2-octanol. An increase to two moles of alkali/mole ricinoleate and a temperature of 250—275°C produces capryl alcohol [123-96-6] CgH gO, and sebacic acid [111-20-6] C QH gO, (39—41). Sebacic acid is used in the manufacture of nylon-6,10. 

Some alcohols that have been converted into the corresponding fluorides by reactions with diethyldminosulfur trifluoride include 1-octanol, 2-methyl-2-butanol, isobutyl alcohol, cyclooctanol, ethylene glycol, crotyl alcohol, 2-phenylethanol, 2-bromoethanol, ethyl lactate, and ethyl a-hydrox3maphthaleneacetate. ... 

Lower aliphatic primary alcohols including octanol, halogeno alcohols, and benzylic alcohols yield only alkyl fluorides [81, 82 The reaction of higher primary alcohols gives a mixture of fluorides and alkyl 2,3,3,3-tetrafluoropropionates [S3] and 2-nitro alcohols, alcohols branched at C-2 [82, 84 and unsaturated alcohols [55] give 2,3,3,3-tetrafluoropropionates exclusively... 

Fig. 7-6). Two unichiral amides which have been known capable of this reaction are 1-phenylethylamine [15] and l-(l-naphthyl)ethylamine [16]. Marfey s reagent [N-a-(2,4-dinitro-5-fluorophenyl)-L-alaninamide] was introduced as a reagent to deriva-tize amino acids with cyclopentane, tetrahydroisoquinoline or tetraline structures [17]. Simple chiral alcohols such as 2-octanol can also be used to derivatize acids such as 2-chloro-3-phenylmethoxypropionic acid [18]. 

One of the most important reasons for using tosylates in S j2 reactions is stereochemical. The S]s]2 reaction of an alcohol via an alkyl halide proceeds with hvo inversions of configuration—one to make the halide from the alcohol and one to substitute the halide—and yields a product with the same stereochemistry as the starting alcohol. The SN2 reaction of an alcohol via a tosylate, however, proceeds with only one inversion and yields a product of opposite stereochemistry to the starting alcohol. Figure 17.5 shows a series of reactions on the R enantiomer of 2-octanol that illustrates these stereochemical relationships. 

Benzenesulfomc acid, 4-methyl, 2,2 dimeth ylpropyl ester [1-Propanol, 2,2-di-methyh, p-toluenesulfonate], 55, 112 Benzenesulfomc acid, 4-methyl-, esters [p-Toluenesulfonates], reaction with organocuprates, 55, 112 Benzenesultonic acid, 4-methyl-, ( )-4-hexen-l-yl ester ]( )-4-Hexen-l-yl p-toluenesulfonate], 55, 57 Benzenesulfomc acid, 4-methyl-, 1-methyl-heptyl ester [2-Octanol, p-toluenesulfonate], 55,112... 

Certain monobutyltin compounds have recently been introduced 561) as esterification catalysts, e.g., in the reaction of phthalic anhydride with octanol to produce dioctyl phthalate. 

Aqueous solutions are not suitable solvents for esterifications and transesterifications, and these reactions are carried out in organic solvents of low polarity [9-12]. However, enzymes are surrounded by a hydration shell or bound water that is required for the retention of structure and catalytic activity [13]. Polar hydrophilic solvents such as DMF, DMSO, acetone, and alcohols (log P<0, where P is the partition coefficient between octanol and water) are incompatible and lead to rapid denaturation. Common solvents for esterifications and transesterifications include alkanes (hexane/log P=3.5), aromatics (toluene/2.5, benzene/2), haloalkanes (CHCI3/2, CH2CI2/I.4), and ethers (diisopropyl ether/1.9, terf-butylmethyl ether/ 0.94, diethyl ether/0.85). Exceptionally stable enzymes such as Candida antarctica lipase B (CAL-B) have been used in more polar solvents (tetrahydrofuran/0.49, acetonitrile/—0.33). Room-temperature ionic liquids [14—17] and supercritical fluids [18] are also good media for a wide range of biotransformations. 

The most limiting factor for enzymatic PAC production is the inactivation of PDC by the toxic substrate benzaldehyde. The rate of PDC deactivation follows a first order dependency on benzaldehyde concentration and reaction time [8]. Various strategies have been developed to minimize PDC exposure to benzaldehyde including fed-batch operation, immobilization of PDC for continuous operation and more recently an enzymatic aqueous/octanol two-phase process [5,9,10] in which benzaldehyde is continuously fed from the octanol to the enzyme in the aqueous phase. The present study aims at optimal feeding of benzaldehyde in an aqueous batch system. 

The reaction between 60% HNO3, octanol, and 3-bromo-2,3-dimethyl propanol proceeds slowly under mechanical stirring at room temperature and gives quantitative yields of the nitrate only after 12 hours. By contrast ultra-sonochemistry (u/s) gives quantitative yields of carboxylic acids in just 20 minutes at room temperature (Pestman et al., 1994). 

The reaction between mono-octyl phthalate and i5tMx tanol (see Fig. 5.4-25) in the presence of a homogeneous catalyst (rert-butyl titanate) was studied in a batch reactor (Szarawara et al., 1991). This is the second step of the reaction between phthalic anhydride and o-octanol. First the ring is opened and mono-octyl phthalate is formed. Water is removed by evaporation as it is formed. The reaction was carried out at 174 °C. The initial concentration of mono-octyl phthalate was cpno = 1.85 mol/L and the ratio of initial concentrations of iio-octanol to mono-ooctyl phthalate coc.o/cph,o = 1.4. The reaction was... 

The pKa of a molecule, a charge-state-related parameter, is a descriptor of an acid-base equilibrium reaction [34,35]. Lipophilicity, often represented by the octanol-water partition coefficient Kp is a descriptor of a two-phase distribution equilibrium reaction [36]. So is solubility [37-39]. These three parameters are thermodynamic constants. On the other hand, permeability Pe is a rate coefficient, a kinetics parameter, most often posed in a first-order distribution reaction [40-42]. 

It is convenient to summarize the various reactions in a box diagram, such as Fig. 4.1 [17,275,280], illustrated with the equilibria of the weak base, propranolol. In Fig. 4.1 is an equation labeled pA °et. This constant refers to the octanol pKa, a term first used by Scherrer [280]. When the concentrations of the uncharged and the charged species in octanol are equal, the aqueous pH at that point defines p which is indicated for a weak acid as... 

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