Isopropyl alcohol selectivity

Hydration of acyclic olefins can be carried out readily with NAFION In a fixed bed tube reactor at 150°C. Because of thermodynamic consideration, propene conversion Is 16% with a Isopropyl alcohol selectivity of 97% (39). 

Although the selectivity of isopropyl alcohol to acetone via vapor-phase dehydrogenation is high, there are a number of by-products that must be removed from the acetone. The hot reactor effluent contains acetone, unconverted isopropyl alcohol, and hydrogen, and may also contain propylene, polypropylene, mesityl oxide, diisopropyl ether, acetaldehyde, propionaldehyde, and many other hydrocarbons and carbon oxides (25,28). 

The vapor-phase reduction of acrolein with isopropyl alcohol in the presence of a mixed metal oxide catalyst yields aHyl alcohol in a one-pass yield of 90.4%, with a selectivity (60) to the alcohol of 96.4%. Acrolein may also be selectively reduced to yield propionaldehyde by treatment with a variety of reducing reagents. 

Typical cosolvents include methanol [67-56-17, ethanol [64-17-5] isopropyl alcohol [67-65-OJ, or toluene. The selection of cosolvents depends on the requirement of the formula and their interaction with other ingredients. Methanol is a common cosolvent in methylene chloride formulas since it has good solvency and is needed to swell ceUulose-type thickening agents. A typical methylene chloride formula used to strip wood is as follows (7). 

Either product can be favored over the other by proper selection of catalyst and reaction conditions. However, the principal source of DIPE is as a by-product from isopropyl alcohol production. Typically, excess DIPE is recycled over acidic catalysts ia the alcohol process where it is hydrated to isopropyl alcohol. DIPE is used to a minor extent ia iadustrial extraction and as a solvent. 

A Hquid-phase variation of the direct hydration was developed by Tokuyama Soda (78). The disadvantages of the gas-phase processes are largely avoided by employing a weakly acidic aqueous catalyst solution of a siHcotungstate (82). Preheated propylene, water, and recycled aqueous catalyst solution are pressurized and fed into a reaction chamber where they react in the Hquid state at 270°C and 20.3 MPa (200 atm) and form aqueous isopropyl alcohol. Propylene conversions of 60—70% per pass are obtained, and selectivity to isopropyl alcohol is 98—99 mol % of converted propylene. The catalyst is recycled and requites Htde replenishment compared to other processes. Corrosion and environmental problems are also minimized because the catalyst is a weak acid and because the system is completely closed. On account of the low gas recycle ratio, regular commercial propylene of 95% purity can be used as feedstock. 

Stratifying water systems for selective extraction of thiocyanate complexes of platinum metals have been proposed. The extraction degree of mthenium(III) by ethyl and isopropyl alcohols, acetone, polyethylene glycol in optimum conditions amounts to 95-100%. By the help of electronic methods, IR-spectroscopy, equilibrium shift the extractive mechanism has been proposed and stmctures of extractable compounds, which contain single anddouble-chai-ged acidocomplexes [Rh(SCN)J-, [Ru(SCN)J, [Ru(SCN)J -have been determined. Constants of extraction for associates investigated have been calculated. 

Acidic ether cleavages are typical nucleophilic substitution reactions, either SN1 or Sn2 depending on the structure of the substrate. Ethers with only primary and secondary alkyl groups react by an S 2 mechanism, in which or Br attacks the protonated ether at the less hindered site. This usually results in a selective cleavage into a single alcohol and a single alkyl halide. For example, ethyl isopropyl ether yields exclusively isopropyl alcohol and iodoethane on cleavage by HI because nucleophilic attack by iodide ion occurs at the less hindered primary site rather than at the more hindered secondary site. 

KHC03, NaOAc, K2HP04, Na3P04, triethyl amine) and finally sodium carbonate was selected as the base of choice. Fluoride initiated Suzuki coupling with KF was unsuccessful. Dimethoxy ether was selected as the solvent after screening a variety of solvents (acetone, tetrahydrofuran, methanol, isopropyl alcohol, and methyl-i-butyl ether). 

The decomposition of methanesulphonyl azide in isopropyl alcohol could be effected by selective irradiation of 2-acetonaphthone instead of benzophenone 21>. Since 2-acetonaphthone triplets are incapable of hydrogen abstraction from isopropyl alcohol 22>, initiation must occur via transfer of excitation energy to the azide. A marked difference was observed from benzophenone sensitization in that the reaction was extremely slow, gave a nitrogen yield of only 68%, and produced a yellow solution 21>. 

The objective of this contribution is to investigate catalytic properties of zeolites differing in their channel systems in transformation of aromatics, i.e. toluene alkylation with isopropyl alcohol and toluene disproportionation. In the former case zeolite structure and acidity is related to the toluene conversion, selectivity to p-cymene, sum of cymenes, and isopropyl/n-propyl toluene ratio. In the latter one zeolite properties are... 

Figure 2 Dependence of toluene conversion and selectivity to p-cymene in toluene alkylation with isopropyl alcohol.

Toluene alkylation with isopropyl alcohol was chosen as the test reaction as we can follow in a detail the effect of zeolite structural parameters on the toluene conversion, selectivity to cymenes, selectivity to para-cymene, and isopropyl/n-propyl ratio. It should be stressed that toluene/isopropyl alcohol molar ratio used in the feed was 9.6, which indicates the theoretical toluene conversion around 10.4 %. As you can see from Fig. 2 conversion of toluene over SSZ-33 after 15 min of T-O-S is 21 %, which is almost two times higher than the theoretical toluene conversion for alkylation reaction. The value of toluene conversion over SSZ-33 is influenced by a high rate of toluene disproportionation. About 50 % of toluene converted is transformed into benzene and xylenes. Toluene conversion over zeolites Beta and SSZ-35 is around 12 %, which is due to a much smaller contribution of toluene disproportionation to the overall toluene conversion. A slight increase in toluene conversion over ZSM-5 zeolite is connected with the fact that desorption and transport of products in toluene alkylation with isopropyl alcohol is the rate controlling step of this reaction [9]... 

In toluene disproportionation the highest toluene conversion was achieved over SSZ-33 due to a high acidity combined with 3-D channel system. High toluene conversion over SSZ-35 results from its strong acidity and large reaction volumes in 18-MR cavities. Toluene conversion in the alkylation with isopropyl alcohol is influenced by a high rate of competitive toluene disproportionation over SSZ-33. ZSM-5 exhibits a high p-selectivity for /7-isopropyl toluene, which seems to be connected with diffusion constraints in the channel system of this zeolite. 

As discussed before, a,P-unsaturated ketones are usually reduced to saturated ketones in isopropyl alcohol as solvent, the reaction proceeding via the enol after H-abstraction by the carbonyl group. When some selected a,p-enones are irradiated in their n-n absorption band (i.e. excitation... 

For the purpose of this case study we will select Isopropyl alcohol as the crystallization solvent and assume that the NRTL-SAC solubility curve for Form A has been confirmed as reasonably accurate in the laboratory. If experimental solubility data is measured in IPA then it can be fitted to a more accurate (but non predictive) thermodynamic model such as NRTL or UNIQUAC at this point, taking care with analysis of the solid phase in equilibrium. As the activity coefficient model only relates to species in the liquid phase we can use the same model with each different set of AHm and Tm data to calculate the solubility of the other polymorphs of Cimetidine, as shown in Figure 21. True polymorphs only differ from each other in the solid phase and are otherwise chemically identical. 

Catalysis experiments were performed to investigate the telomerization of butadiene with ethylene glycol in selected TMS systems (e.g. si toluene DMF 1 5 4 or sl 2-octanol DMSO 1.35 3 5.2). With Pd/TPPTS as the catalyst a maximum yield of only 10% of the desired products could be achieved. With Pd/TPPMS the yield increased up to 43% in the TMS system si toluene isopropyl alcohol, but additional water had to be added to obtain a phase split after the reaction. The catalyst leaching is very high and 29% of the palladium used is lost to the product phase. 

Another potential application for zeolite/polymer mixed-matrix membranes is the separation of various liquid chemical mixtures via pervaporation. Pervapora-tion is a promising membrane-based technique for the separation of liquid chemical mixtures, especially in azeotropic or close-boihng solutions. Polydime thy 1-siloxane (PDMS), which is a hydrophobic polymer, has been widely used as the continuous polymer matrix for preparing hydrophobic mixed-matrix membranes. To achieve good compatibility and adhesion between the zeolite particles and the PDMS polymer, ZSM-5 was incorporated into the PDMS polymer matrix, the resulting ZS M -5/ P DM S mixed-matrix membranes showed simultaneous enhancement in selectivity and flux for the separation of isopropyl alcohol from water. It was demonstrated that the separation performance of these membranes was affected by the concentration of the isopropyl alcohol in the feed [96]. 

Another type of mixed-matrix membranes for alcohol/water pervaporation applications was developed utilizing hydrophiUc poly(vinyl alcohol) (PVA) and ZSM-5. The ZSM-5/PVA mixed-matrix membranes demonstrated increased selectivity and flux, compared to pure PVA, for the water/isopropyl alcohol separation [97]. This type of mixed-matrix membranes, however, may have membrane swelling issue due to the hydrophilic nature of the PVA polymer. Mixed-matrix membranes comprising modifled poly(vinyl chloride) and NaA zeolite have shown both enhanced flux and selectivity for the ethanol/water separation at high NaA loadings [98]. 

Several reagents reduce aldehydes preferentially to ketones in mixtures of both. Very high selectivity was found in reductions using dehydrated aluminum oxide soaked with isopropyl alcohol and especially diisopropylcarbinol [755], or silica gel and tributylstamane [756]. The best selectivity was achieved with lithium trialkoxyalumimm hydrides at —78°. In the system hexanal/ cyclohexanone the ratio of primary to secondary alcohol was 87 13 at 0° and 91.5 8.5 at —78° with lithium tris(/er/-butoxy)aluminum hydride [752], and 93.6 6.4 at 0° and 99.6 0.4 at —78° with lithium tris(3-ethyl-3-pentyl-oxy)aluminum hydride [752],... 

Since sodium borohydride usually does not reduce the nitrile function it may be used for selective reductions of conjugated double bonds in oc,/l-un-saturated nitriles in fair to good yields [7069,1070]. In addition some special reagents were found effective for reducing carbon-carbon double bonds preferentially copper hydride prepared from cuprous bromide and sodium bis(2-methoxyethoxy)aluminum hydride [7766], magnesium in methanol [7767], zinc and zinc chloride in ethanol or isopropyl alcohol [7765], and triethylam-monium formate in dimethyl formamide [317]. Lithium aluminum hydride reduced 1-cyanocyclohexene at —15° to cyclohexanecarboxaldehyde and under normal conditions to aminomethylcyclohexane, both in 60% yields [777]. 

There remains little more for the operator to decide. Sometimes, alternative but similar solvent mixtures that have a lower viscosity or higher solute diffusivity could be selected. For example, a n-hexane/methanol mixture might be chosen as an alternative to the more viscous n-heptane/isopropyl alcohol mixture as it has similar elution properties. However, it will be shown later, that if a fully optimized column is employed the viscosity of the mobile phase does not seem to effect the column performance as it is taken into account in the optimization procedure. The operator would, under some circumstances, be free to choose less toxic or less costly solvents for example, in reverse phase chromatography the operator could select methanol/ water solvent mixtures as opposed to acetonitrile/water mixture on the basis of lower cost or less... 

In conclusion, we have found a convenient and practical method for the selective reduction of C=0 bond of a wide spectrum of a-keto-)S, -unsaturated esters with Ru(p-cymene)(TsDPEN) as catalyst. The transition metal catalyzed transfer hydrogenation reaction with good selectivity and high efficiency offers possibilities to provide the optically active a-hydroxy-/l, y-unsaturated esters with chiral catalysts. Table 3.8 gives different substrates that can be reduced with Ru(p-cymene) (TsDPEN) complex in isopropyl alcohol. 

Solid superacidic Nafion-H was also found to be effective in the hydration of acyclic alkenes.16 Isopropyl alcohol was produced with 97% selectivity in hydrating propylene17 at 150°C, whereas isobutylene yielded tert-butyl alcohol18 with 84% selectivity at 96°C. 

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