Phenylethanols, dehydration

The hydroperoxide process involves oxidation of propjiene (qv) to propylene oxide by an organic hydroperoxide. An alcohol is produced as a coproduct. Two different hydroperoxides are used commercially that result in / fZ-butanol or 1-phenylethanol as the coproduct. The / fZ-butanol (TBA) has been used as a gasoline additive, dehydrated to isobutjiene, and used as feedstock to produce methyl tert-huty ether (MTBE), a gasoline additive. The 1-phenyl ethanol is dehydrated to styrene. ARCO Chemical has plants producing the TBA coproduct in the United States, Erance, and the Netherlands. Texaco has a TBA coproduct plant in the United States. Styrene coproduct plants are operated by ARCO Chemical in the United States and Japan, Shell in the Netherlands, Repsol in Spain, and Yukong in South Korea. 

After epoxidation, propylene oxide, excess propylene, and propane are distilled overhead. Propane is purged from the process propylene is recycled to the epoxidation reactor. The bottoms Hquid is treated with a base, such as sodium hydroxide, to neutralize the acids. Acids in this stream cause dehydration of the 1-phenylethanol to styrene. The styrene readily polymerizes under these conditions (177—179). Neutralization, along with water washing, allows phase separation such that the salts and molybdenum catalyst remain in the aqueous phase (179). Dissolved organics in the aqueous phase ate further recovered by treatment with sulfuric acid and phase separation. The organic phase is then distilled to recover 1-phenylethanol overhead. The heavy bottoms are burned for fuel (180,181). 

The coproduct 1-phenylethanol from the epoxidation reactor, along with acetophenone from the hydroperoxide reactor, is dehydrated to styrene in a vapor-phase reaction over a catalyst of siUca gel (184) or titanium dioxide (170,185) at 250—280°C and atmospheric pressure. This product is then distilled to recover purified styrene and to separate water and high boiling organics for disposal. Unreacted 1-phenylethanol is recycled to the dehydrator. 

Acetophenone is separated for hydrogenation to 1-phenylethanol, which is sent to the dehydrator to produce styrene. Hydrogenation is done over a fixed-bed copper-containing catalyst at 115—120°C and pressure of 8100 kPa (80 atm), a 3 1 hydrogen-to-acetophenone ratio, and using a solvent such as ethylbenzene, to give 95% conversion of the acetophenone and 95% selectivity to 1-phenylethanol (186,187). 

PO—SM Coproduction. The copioduction of propylene oxide and styrene (40—49) includes three reaction steps (/) oxidation of ethylbenzene to ethylbenzene hydroperoxide, (2) epoxidation of ethylbenzene hydroperoxide with propylene to form a-phenylethanol and propylene oxide, and (3) dehydration of a-phenylethanol to styrene. 

It is carried out in the Hquid phase at 100—130°C and catalyzed by a soluble molybdenum naphthenate catalyst, also in a series of reactors with interreactor coolers. The dehydration of a-phenylethanol to styrene takes place over an acidic catalyst at about 225°C. A commercial plant (50,51) was commissioned in Spain in 1973 by Halcon International in a joint venture with Enpetrol based on these reactions, in a process that became known as the Oxirane process, owned by Oxirane Corporation, a joint venture of ARCO and Halcon International. Oxirane Corporation merged into ARCO in 1980 and this process is now generally known as the ARCO process. It is used by ARCO at its Channelview, Texas, plant and in Japan and Korea in joint ventures with local companies. A similar process was developed by Shell (52—55) and commercialized in 1979 at its Moerdijk plant in the Netherlands. The Shell process uses a heterogeneous catalyst of titanium oxide on siHca support in the epoxidation step. Another plant by Shell is under constmction in Singapore (ca 1996). 

A three-step process involving the oxidation of acetophenone, hydrogenation of the ketone to a-phenylethanol, and dehydration of the alcohol to styrene was practiced commercially by Union Carbide (59) until the early 1960s. Other technologies considered during the infancy of the styrene industry include side-chain chlorination of ethylbenzene followed by dehydrochlotination or followed by hydrolysis and dehydration. 

Reaction of Ser-OMe with benzimino ethyl ester resulted in the formation of an oxazoline without racemization (Scheme 27) (85T2379). After forming an amide with 2-amino-l-phenylethanol, Af-phthalimido AAs were oxidized with CrOs and dehydrated by POCI3 to give substituted oxazoles (91JHC1241). 

EB/SM (ethylbenzene/styrene monomer) process. Styrene can also be made by PO/SM (propylene oxide/styrene monomer) process). This process starts by oxidizing ethylbenzene (C6H5CH2CH2) to its hydroperoxide (C6H5CH(OOH)CH3), which is then used to oxidize propylene (CH3CH = CH2) to produce propylene oxide (CH3CH2CHO) and phenylethanol (C6H5CH(OH)CH3). The phenylethanol is then dehydrated to give... 

The additional advantage of this process is the possibility of the utilization of the alcohol products. fcrf-BuOH (and MTBE, its methyl ether) is used as a gasoline additive. It can be dehydrated to yield isobutylene, which is used to produce high-octane alkylates (see Section 5.5.1). 1-Phenylethanol is dehydrated to styrene over Ti02 on alumina.919... 

In some cases, the effect of reactant structure may outweigh the influence of catalyst nature. This is seen by comparison with the dehydration of aliphatic secondary alcohols and substituted 2-phenylethanols on four different oxide catalysts (Table 4). With aliphatic alcohols, the slope of the Taft correlation depended on the nature of the catalyst (A1203 + NaOH 1.2, Zr02 0.3, Ti02—0.8, Si02—2.8 [55]) whereas for 2-phenyl-ethanols, the slope of the corresponding Hammett correlation had practically the same value (from —2.1 to —2.4) for all catalysts of this series [95]. The resonance stabilisation of an intermediate with a positive charge on Ca clearly predominates over other influences. 

The transformation was called an homologation reaction because essentially it consisted in going from one alcohol to an alcohol containing one carbon atom more than the starting material (Wender, Levine, and Orchin, 14). Tertiary alcohols reacted most rapidly, secondary alcohols less rapidly and primary alcohols only very slowly. It was of considerable importance to ascertain whether the olefin intermediate was essential and for this purpose, methanol and benzyl alcohol, neither of which can dehydrate to an olefin, were used in the reaction. Both compounds, contrary to other primary alcohols, reacted quite rapidly and gave the homologous alcohol of the methanol converted, about 40 mole per cent went to ethanol and with benzyl alcohol, a 30% yield of 2-phenylethanol was secured. In both examples, however, reduction products were also present of the methanol converted, 8 mole per cent went to methane and from benzyl alcohol, a 50 to 60% yield of toluene was secured. The conversion of methanol to methane appears to be the only case in which an appreciable quantity of hydrocarbon is secured from a purely aliphatic alcohol. The behavior of benzyl alcohol and its derivatives will be discussed later. 

We know that because of resonance stabilization (Sec. 12.19) the benzyl cation should be an extremely stable ion, and so we are not surprised to find that an alcohol such as 1-phenylethanol (like a tertiary alcohol) undergoes dehydration extremely rapidly. 

Thus the homologation reaction can be used, for example, for the synthesis of acetaldehyde from methanol [48], propionic acid from acetic acid [47], or ethyl acetate from methyl acetate [50]. Styrene may be produced from toluene by oxidation to benzyl alcohol [51] and homologation to 2-phenylethanol, which in turn can be dehydrated to styrene. From the chemical point of view, the applications of homologation reactions are broad and useful. But, as mentioned before, low selec-... 

The first step is oxidation of EB to form EB hydroperoxide. The oxidation is carried out in the liquid phase with a target EB conversion of approximately 13%. Although higher conversions are attractive from an EB recovery and recycle standpoint, there is a significant disadvantage because the EB hydroperoxide selectivity declines sharply. The second step is epoxidation of propylene to form propylene oxide product and 1-phenylethanol. In the last step, the 1-phenylethanol is dehydrated to styrene and water. The dehydrated reaction mixture is typically stripped of light components and rerun in a styrene column to remove heavy by-products, resulting in a purified styrene product. 

Dehydration of cyclohexanol, 2-methyl cyclohexanol, 2-phenylethanol Hydrolysis Water Acid... 

Lithiation of the methyl of (methylthio)benzene followed by acylation with an acyl chloride and acidification to pH 4-5 yields benzothiophene in good yields, but when aroyl chlorides are used, the mixture has to be heated in benzene. An attempted dehydration of the secondary alcohol (87.4) with hydrobromic acid led to S-demethylation and cyclization. Similar treatment of the isomeric 2-(2-methy thio-4-nitrophenyl)-l-phenylethanol gave a high yield of 6-nitro-2-phenyl-2,3-dihydrobenzo[fi]thiophene [2653]. 

The hydroperoxide formed by the air oxidation of ethylbenzene is used to convert propylene to its oxide. The byproduct 1-phenylethanol is dehydrated to styrene, a second valuable product. The disadvantage of such a process is that the demand for such products has to be equal on a molar basis. 

Fig. 7. Correlation of dehydration of 1-phenylethanols over alumina catalyst at 210° (41) by the Hammett equation.

The operations in Spain and Japan use ethylbenzene as the hydrocarbon feedstock for oxidation. The co-produced alcohol, 1-phenylethanol, is dehydrated to styrene (phenylethene, section 12.11.1). This version is now also used in Arco s latest U.S. plant, commissioned in late 1991. 

The elimination can be subject to general base catalysis. Loudon and Noyce found general base catalysis in the dehydration of substituted l-aryl-2-phenylethanols in aqueous dioxane solution with 1 1 dichloroacetic add-soditun dichloroacetate buffers. Loudon, G. M. Noyce, D. S. /. Am. Chem. Soc. 1%9, 91,1433. 

STRATEGY AND ANSWER Working backward we realize we could synthesize 2-phenylethanol by hydroboration-oxidation of phenylethene (styrene), and that we could make phenylethene by dehydrating 1-phenylethanol. 

The indirect propylene oxidation process via ethylbenzene hydroperoxide (Halcon process) is displayed in Eq. (6.12.12). Ethylbenzene, obtained by the acid-catalyzed Friedel-Crafts alkylation of benzene with ethylene, is converted with air into ethylbenzene hydroperoxide. The hydroperoxide epoxidizes propylene and generates the co-product a-phenylethanol that is later dehydrated to styrene. Styrene is a major industrial chemical used mainly as monomer for polymers such as polystyrene or styrene-containing copolymers ... 

In the peroxidation reactor ethylbenzene is converted with air at 146 °C and 2 bar to form a 12-14 wt% solution of ethylbenzene hydroperoxide in ethylbenzene. The reaction takes place in the liquid phase and conversion is limited to 10% for safety reasons. The reactor is a bubble tray reactor with nine separate reaction zones. To avoid decomposition of the formed peroxide the temperature is reduced from 146 °C to 132 °C over the trays. In the epoxidation reactor the reaction solution is mixed with a homogeneous molybdenum naphthenate catalyst. Epoxidation of propylene in the liquid phase is carried out at 100-130 °C and 1-35 bar. The crude product stream (containing PO, unreacted propylene, a-phenylethanol, acetophenone, and other impurities) is sent to the recycle column to remove propylene. The catalyst can be removed by an aqueous alkali wash and phase separation. The crude PO, obtained as head stream in the crude PO column, is purified by distillations. The unconverted reactant ethylbenzene can be recycled in the second recycle column. The bottom stream containing a-phenylethanol is sent to the dehydration reactor. The vapor-phase dehydration of a-phenylethanol to styrene takes place over a titanium/alumina oxide catalyst at 200-280 °C and 0.35 bar (conversion 85%, selectivity 95%). 

The similarity of the boiling points of ethyl benzene (136 C) and styrene (145-2T) and the tendency of the latter to polymerize make the necessary purification stage difficult. This has encouraged the exploration of other possible routes which although apparently longer provide simpler purification stages. One such route involves oxidation of ethyl benzene to a-phenyl ethanol, acetophenone and by-products. The acetophenone is hydrogenated to the alcohol and the combined phenylethanol stream dehydrated to styrene. In this process the economics depend on the successful use of the by-products formed. 

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