Oxirane reactions oxidation

In selective etherification, it is important to distinguish between reversible and irreversible reactions. The former class comprises etherifications with dimethyl sulfate, halogen compounds, oxirane (ethylene oxide), and diazoalkanes, whereas the latter class involves addition reactions of the Michael type of hydroxyl groups to activated alkenes. In this Section, irreversible and reversible reactions are described separately, and a further distinction is made in the former group by placing the rather specialized, diazoalkane-based alkylations in a separate subsection. 

So far, no reference has been made to the presence of more than one phase in the reactor. Many important chemicals are manufactured by processes in which gases react on the surface of solid catalysts. Examples include ammonia synthesis, the oxidation of sulphur dioxide to sulphur trioxide, the oxidation of naphthalene to phthalic anhydride and the manufacture of methanol from carbon monoxide and hydrogen. These reactions, and many others, are carried out in tubular reactors containing a fixed bed of catalyst which may be either a single deep bed or a number of parallel tubes packed with catalyst pellets. The latter arrangement is used, for exjimple, in the oxidation of ethene to oxiran (ethylene oxide)... 

Figure 15-5 Important commercial reactions of oxacyclopropane (oxirane, ethylene oxide)...

The first set of reactions is the mainstay of the petrochemical industry 1 outstanding examples are the oxidation of propene to propenal (acrolein) catalysed by bismuth molybdate, and of ethene to oxirane (ethylene oxide) catalysed by silver. In general these processes work at high but not perfect selectivity, the catalysts having been fine-tuned by inclusion of promoters to secure optimum performance. An especially important reaction is the oxidation of ethene in the presence of acetic (ethanoic) acid to form vinyl acetate (ethenyl ethanoate) catalysed by supported palladium-gold catalysts this is treated in Section 8.4. Oxidation reactions are very exothermic, and special precautions have to be taken to avoid the catalyst over-heating. 

Corey and Chaykovsky26 give a detailed description of the preparation of the reagent from trimethyloxosulfonium iodide, dimethyl sulfoxide, and sodium hydride, and for its reaction with cyclohexanone to form the oxirane methylenecyclohexane oxide. 

There is no unique isodesmic reaction for a particular problem. For example, to compare the ring strain in oxacyclopropane (oxirane, ethylene oxide) with that in cyclopropane, one might calculate the reaction energy ofthe oxygen exchange reaction (remember that isodesmic reactions do not have to be experimentally achievable) ... 

Oxiranes (a-oxides, a-epoxides) are known to polymerize by cationic and anionic mechanisms as well as by ionic-coordinative reactions 1 3). Their ability of ring opening by one of these processes depends mainly on the structure and number of substituents. Some examples are given below ... 

It might be expected that oxacycloalkanes as oxirane (ethylene oxide) would undergo a similar reaction and, indeed, a new chapter in the chemistry of ethers is... 

For these and a variety of special non-food purposes esters with higher fatty acids, succinic, adipic and citric acids and carbamates (reaction products with urea), have also been prepared. Examples of starch ethers are 2-hydroxyethyl and 2-hydroxypropyl starches prepared by reaction of starch with oxirane (ethylene oxide) and methyloxirane (propylene-l,2-oxide). The reaction occurs preferentially at the secondary hydroxyl groups at C-2, with less on the C-3 and C-6 hydroxyl groups. The most common products are those shown in Figure 4.15. The degree of substitution tends to be <0.2. According to the reaction conditions, polyoxaalkyl starches ... 

Mono- and disaccharides are highly hydrophilic substances. They are produced in large volumes, are available in highly pure form, and are relatively cheap [4,5]. They may be, and indeed have been, used as hydrophilic substrates for the synthesis of nonionic surfactants. In 1999, the worldwide production of the latter was about 3.6 3.8 million metric tons, i.e., approximately 38% of total surfactant production [6]. The majority of the conventional nonionic surfactants are oligooxyethylene (and oxypropylene) chain-containing compounds obtained in the reaction of oxirane (ethylene oxide) or methyloxirane (propylene oxide) with hydrophobic intermediates that contain a functional group with an active hydrogen atom [7]. Only recently, the direct reaction of oxirane with fatty acid methyl esters in the... 

With methyl oxirane, propylene oxide, ring opening is by cleavage of the less-substituted carbon-to-oxygen bond. Since the terminal oxyalkanol groups are still active, the polymerizations, as represented, are "living" polymerization reactions. However, there are termination side reactions that become particularly important at elevated reaction temperatures. 

These reactions are rapid and the sulfide is efficiently oxidized to sulfoxide as the only product with no over-oxidation to sulfone. The oxirane reaction [Eq. (1)] is thought to proceed via a direct oxygen transfer from the oxirane to the sulfide. In a recent mechanistic study [9] it was found that a hypervalent sulfurane is an intermediate in the oxidation of sulfides by dioxiranes. This intermediate is in equih-brium with the electrophilic zwitterionic intermediate formed as a result of electrophilic attack by the peroxide on the sulfide. 

Ethylenic compounds when oxidised with perbenzoic acid or perphthalic acid in chloroform solution yield epoxides (or oxiranes). This Is sometimes known as the Prileschajew epoxidation reaction. Thus pyrene affords styrene oxide (or 2-plienyloxirane) ... 

The most general methods for the syntheses of 1,2-difunctional molecules are based on the oxidation of carbon-carbon multiple bonds (p. 117) and the opening of oxiranes by hetero atoms (p. 123fl.). There exist, however, also a few useful reactions in which an a - and a d -synthon or two r -synthons are combined. The classical polar reaction is the addition of cyanide anion to carbonyl groups, which leads to a-hydroxynitriles (cyanohydrins). It is used, for example, in Strecker s synthesis of amino acids and in the homologization of monosaccharides. The ff-hydroxy group of a nitrile can be easily substituted by various nucleophiles, the nitrile can be solvolyzed or reduced. Therefore a large variety of terminal difunctional molecules with one additional carbon atom can be made. Equally versatile are a-methylsulfinyl ketones (H.G. Hauthal, 1971 T. Durst, 1979 O. DeLucchi, 1991), which are available from acid chlorides or esters and the dimsyl anion. Carbanions of these compounds can also be used for the synthesis of 1,4-dicarbonyl compounds (p. 65f.). 

An oxirane process utilizes ethylbenzene to make the hydroperoxide, which then is used to make propylene oxide [75-56-9]. The hydroperoxide-producing reaction is similar to the first step of cumene LPO except that it is slower (2,224,316—318). In the epoxidation step, a-phenylethyl alcohol [98-85-1] is the coproduct. It is dehydrated to styrene [100-42-5]. The reported 1992 capacity for styrene by this route was 0.59 X 10 t/yr (319). The corresponding propylene oxide capacity is ca 0.33 x 10 t/yr. The total propylene oxide capacity based on hydroperoxide oxidation of propylene [115-07-1] (coproducts are /-butyl alcohol and styrene) is 1.05 x 10 t/yr (225). 

The second process involves reaction of propylene with peroxides, as in the Oxirane process (97), in which either isobutane or ethylbenzene is oxidized to form a hydroperoxide. 

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). 

Nucleophilic attack on oxirane carbon usually proceeds with inversion of configuration (Scheme 44) as expected for Sn2 reactions, even under acid conditions (Scheme 45). Scheme 45 also illustrates the fact that cyclohexene oxides open in a fran5-diaxial manner this is known as the Fiirst-Plattner rule (49HCA275) and there are very few exceptions to it. 

Electron deficient carbon-carbon double bonds are resistant to attack by the electrophilic reagents of Section 5.05.4.2.2(t), and are usually converted to oxiranes by nucleophilic oxidants. The most widely used of these is the hydroperoxide ion (Scheme 79). Since epoxidation by hydroperoxide ion proceeds through an intermediate ct-carbonyl anion, the reaction of acyclic alkenes is not necessarily stereospecific (Scheme 80) (unlike the case of epoxidation with electrophilic agents (Section 5.05.4.2.2(f)) the stereochemical aspects of this and other epoxidations are reviewed at length in (B-73MI50500)). 

In analogy with the peracid attack on steroidal double bonds, the formation of the bromonium ion, e.g., (81a), occurs from the less hindered side (usually the a-side of the steroid nucleus) to give in the case of the olefin (81) the 9a-bromo-l l -ol (82). Base treatment of (82) provides the 9 5,1 l S-oxide (83). Similarly, reaction of 17/3-hydroxyestr-5(10)-en-3-one (9) with A -bromosuccinimide-perchloric acid followed by treatment with sodium hydroxide and sodium borohydride furnishes the 3, 17 5-dihydroxy-5a,l0a-oxirane. As mentioned previously, epoxidation of (9) with MPA gives the 5, 10 -oxirane. °... 

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