Catalysts ether formation

Mobil MTG and MTO Process. Methanol from any source can be converted to gasoline range hydrocarbons using the Mobil MTG process. This process takes advantage of the shape selective activity of ZSM-5 zeoHte catalyst to limit the size of hydrocarbons in the product. The pore size and cavity dimensions favor the production of C-5—C-10 hydrocarbons. The first step in the conversion is the acid-catalyzed dehydration of methanol to form dimethyl ether. The ether subsequendy is converted to light olefins, then heavier olefins, paraffins, and aromatics. In practice the ether formation and hydrocarbon formation reactions may be performed in separate stages to faciHtate heat removal. 

Transesterification of methyl methacrylate with the appropriate alcohol is often the preferred method of preparing higher alkyl and functional methacrylates. The reaction is driven to completion by the use of excess methyl methacrylate and by removal of the methyl methacrylate—methanol a2eotrope. A variety of catalysts have been used, including acids and bases and transition-metal compounds such as dialkjitin oxides (57), titanium(IV) alkoxides (58), and zirconium acetoacetate (59). The use of the transition-metal catalysts allows reaction under nearly neutral conditions and is therefore more tolerant of sensitive functionality in the ester alcohol moiety. In addition, transition-metal catalysts often exhibit higher selectivities than acidic catalysts, particularly with respect to by-product ether formation. 

Reactions of the Side Chain. Benzyl chloride is hydrolyzed slowly by boiling water and more rapidly at elevated temperature and pressure in the presence of alkaHes (11). Reaction with aqueous sodium cyanide, preferably in the presence of a quaternary ammonium chloride, produces phenylacetonitrile [140-29-4] in high yield (12). The presence of a lower molecular-weight alcohol gives faster rates and higher yields. In the presence of suitable catalysts benzyl chloride reacts with carbon monoxide to produce phenylacetic acid [103-82-2] (13—15). With different catalyst systems in the presence of calcium hydroxide, double carbonylation to phenylpymvic acid [156-06-9] occurs (16). Benzyl esters are formed by heating benzyl chloride with the sodium salts of acids benzyl ethers by reaction with sodium alkoxides. The ease of ether formation is improved by the use of phase-transfer catalysts (17) (see Catalysis, phase-thansfer). 

The data of Nishimura et al. (68) emphasize how strongly ether formation depends on the catalyst. 

Crosslinking resoles in the presence of sodium carbonate or potassium carbonate lead to preferential formation of ortho-ortho methylene linkages.63 Resole networks crosslinked under basic conditions showed that crosslink density depends on the degree of hydroxymethyl substitution, which is affected by the formaldehyde-to-phenol ratio, the reaction time, and the type and concentration of catalyst (uncatalyzed, with 2% NaOH, with 5% NaOH).64 As expected, NaOH accelerated the rates of both hydroxymethyl substitution and methylene ether formation. Significant rate increases were observed for ortho substitutions as die amount of NaOH increased. The para substitution, which does not occur in the absence of the catalyst, formed only in small amounts in the presence of NaOH. 

O- versus C-a kyIation product ratios in the methylation of desoxybenzoin by dimethyl sulphate can be varied between 0.75 and 63 by the choice of catalyst. The reaction can be steered towards enol-ether formation by large, sterically shielded ammonium ions, while C-alkylation is favoured by small ammonium ions (e.g. RMejN" ) and by crown ethers (Dehmlow and Schrader, 1990). 

It is in the very nature of the catalytic process that the intermediate compound formed between catalyst and reactant is of extreme lability therefore not many cases are on record where the isolation by chemical means, or identification by physical methods, of intermediate compounds has been achieved concomitant with the evidence that these compounds are true intermediaries and not products of side reactions or artifacts. The formation of ethyl sulfuric acid in ether formation, catalyzed by HjSO , and of alkyl phosphates in olefin polymerization, catalyzed by liquid phosphoric acid, are examples of established intermediate compound formation in homogeneous catalysis. With regard to heterogeneous catalysis, where catalyst and reactant are not in the same... 

The oxonium ylide mechanism requires a bifunctional acid-base catalyst. The validity of the oxonium ylide mechanism on zeolites was questioned459,461,464 because zeolites do not necessarily possess sufficiently strong basic sites to abstract a proton from the trimethyloxonium ion to form an ylide. It should, however, be pointed out, as emphasized by Olah,447,465 that over solid acid-base catalysts (including zeolites) the initial coordination of an electron-deficient (i.e., Lewis acidic) site of the catalysts allows formation of a catalyst-coordinated dimethyl ether complex. It then can act as an oxonium ion forming the catalyst-coordinated oxonium ylide complex (10) with the participation of surface bound CH30 ions ... 

The best catalysts for olefin hydration are not necessarily those which have proved most satisfactory for the reverse reaction. Some of the successful hydration catalysts are not typical dehydration catalysts. The more obvious reasons are (i) different adsorption characteristics of the catalyst is desirable, e.g. stronger adsorption of olefin relative to alcohol, (ii) under the conditions used for the hydration, ether formation cannot be suppressed as readily as in the dehydration, (iii) at high pressures, the olefins tend to polymerise much more than at the low pressures used for the dehydration. 

Traditionally, ethanol has been made from ethylene by sulfation followed by hydrolysis of the ethyl sulfate so produced. This type of process has the disadvantages of severe corrosion problems, the requirement for sulfuric acid reconcentration, and loss of yield caused by ethyl ether formation. Recently a successful direct catalytic hydration of ethylene has been accomplished on a commercial scale. This process, developed by Veba-Chemie in Germany, uses a fixed bed catalytic reaction system. Although direct hydration plants have been operated by Shell Chemical and Texas Eastman, Veba claims technical and economic superiority because of new catalyst developments. Because of its economic superiority, it is now replacing the sulfuric acid based process and has been licensed to British Petroleum in the United Kingdom, Publicker Industries in the United States, and others. By including ethanol dehydrogenation facilities, Veba claims that acetaldehyde can be produced indirectly from ethylene by this combined process at costs competitive with the catalytic oxidation of ethylene. 

Clearly, much more information is needed about the behaviour of these two monomers and oxacyclobutane is perhaps the more favorable for further study because of its clearer catalyst-co-catalyst relationship and the absence of vinyl ether formation. The particular information needed about oxacyclobutane reactions at the present time are (a) knowledge of the fate of the catalyst, (b) viscosity-molecular weight relationship, (c) much more information about the variation of molecular weight with the reaction variables, and (d) information about the reaction of both monomer and polymer with oxonium ions and about the ease of formation of oxonium ions by oxacyclobutane. 

Friedel-Crafts alkylation of benzene,220 221 toluene,222para-xylene,220 and naphthalene223 with benzyl alcohols have been studied over Nafion-silica nano-composite catalysts, including the kinetics of alkylation.221,223 In most cases, 13% Nafion-silica showed the highest activity, testifying again to the much higher accessibility of the active sites. Complete conversion of para-xylene was found in the presence of triflic acid, and it was the only reaction when ether formation as side reaction did not occur. 

It seemed prudent that the same ethers be examined in the absence of potentially labile functionality, thus removal of unsaturation in 262 and 263 was considered. Hydrogenation of 259 over Pd/C or Pt was unsuccessful in either case reduction of the peroxide group was problematical. Hydrogenation over Wilkinson s catalyst gave a new product, but with the unsaturation retained. While selective alkene hydrogenation can sometimes be achieved in the presence of a peroxide bond, the double bond of 259 was apparently too hindered in this case. Diimide, on the other hand, worked reasonably well for this reduction. Thus, treatment of 259 in dichlo-romethane solution with potassium azodicarboxylate followed by addition of acetic acid led, after several days, to roughly 60% conversion of 259 to the saturated version, 264. Now, ether formation as before provided the saturated methyl and benzyl ethers 265 and 266, respectively, in good yields. 

Similar properties and applications as for HMDS useful for amino acid analyses provides good response for electron capture detection has relatively low silyl donating ability and is usually used in the presence of a base such as pyridine may cause enol-ether formation with unprotected ketone groups often used as a catalyst with other silylating reagents... 

Catalytic alcoholysis of silanes by a variety of transition metal based catalysts is a useful method to form silyl ethers under mild conditions (Scheme 19). The process is atom-economical hydrogen gas is the only byproduct. This mild method has not been fully exploited for the preparation of unsymmetrical bis-alkoxysilanes. A catalytic synthesis using silicon alcoholysis would circumvent the need of bases (and the attendant formation of protic byproducts), and eliminate the need for excess silicon dichlorides in the first silyl ether formation. We sought catalytic methods that would ultimately allow formation of chiral tethers that are asymmetric at the silicon center (Scheme 20). Our method, once developed, should be easily transferable for use with high-value synthetic intermediates in a complex target-oriented synthesis therefore, it will be necessary to evaluate the scope and limitation of our new method. 

The difference in initial slope is attributed to the different number of catalytic sites involved in the two reactions. If water is stripped from the liquid, coverage of the catalyst surface with water molecules decreases, and in consequence both reactions are running faster. However, the increase of ether formation is proportional to the square of the progress of the esterification, because of the square in the adsorption term in the ether rate expression (3). Therefore, stripping of water increases the rates, but lowers the selectivity at low conversion levels. 

This section deals with the conceptual design of a catalytic distillation process for the esterification of lauric acid (LA) with 2-ethyl-hexanol (2EtH). Laboratory experiments showed that a superacid sulfated zirconia catalyst exhibits good activity over a large interval, from 130 to 180 °C with no ether formation. On the contrary, the catalyst is sensitive to the presence of free liquid water. Raw materials are lauric acid and 2-ethylhexyl alcohol of high purity. The conversion should be over 99.9%, because the product is aimed at cosmetic applications. 

Treatment of the ion-exchanged RhNaX catalyst with hydrogen (205) results in almost complete reduction of Rh3+ to Rh° with a consequent much reduced carbonylation activity, whereas ether formation remains virtually unaffected. These results demonstrate that the dehydration activity is a function of the support only and that cationic rather than zero-valent rhodium is the active entity for the carbonylation reaction. 

MTBE is produced by reacting methanol and isobutylene under mild conditions in the presence of an acid catalyst. The isobutylene feed is either mixed butylenes, a butylenes stream from catalytic cracking, or a butylenes coproduct from ethylene production. The reaction conditions are mild enough to permit the n-butenes to pass through without ether formation. Figure 10.31 shows a typical process for making MTBE. 

The Degussa process (now owned by Dupont) starts from acrolein, which is hydrated in the presence of an acidic ion exchanger into 3-hydroxypropanal (3HP, Fig. 8.8 a). The latter is subsequently extracted into isobutyl alcohol and hydrogenated over a Ni catalyst [53]. The overall yield does not exceed 85%, due to competing water addition at the 2-position and ether formation in the initial step. It has been announced that Degussa will supply up 10 kt a-1 to Dupont until the fermentative process of the latter company (see below) comes on stream [54]. 

An orf/io-directed lithiation allows the conversion of 25 to aryl iodide 40. Reductive ether formation of aldehyde 40 with crotyl alcohol yields compound 41. Intramolecular Heck reaction of 41 affords a mixture of the olefins 42 and 43. The undesired alkene 42 can be isomer-ized quantitatively to the desired enol ether 43 with Wilkinson s catalyst. Sharpless dihydroxylation ee 94 %) of the enol ether 43 provides lactol 44, which is oxidized directly to lactone 45. Finally, the pyridone-O-methyl ester is cleaved under acid conditions (45 — 7). 

DBSA is also applicable to other reactions in water. Ether formation from two alcohols is such an example [40]. We tried formation of symmetric ethers from benzylic alcohols in water using 10 mol% of DBSA as a catalyst. The reactions were found to proceed smoothly in water to afford the corresponding symmetric ethers in high yields (Table 13.8, entries 1 and 2). It should be noted that the etherification of the substrate shown in entry 1 in the presence of TsOH instead of DBSA gave only a trace amount... 

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