Propylene oxide allyl alcohol from

An example of this t3T)e of reaction which does not produce a byproduct is the production of allyl alcohol from propylene oxide ... 

A soln. of cyclooctene oxide in benzene passed at 180 with the aid of Ng through a column packed with Li-orthophosphate pellets 3-hydroxycyclooctene. Y 70%. - Li-diethylamide causes mostly rearrangement to 2-hydroxybicyclo[3.3.0]-octane. M. N. Sheng, Synthesis 1972, 194 allyl alcohol from propylene oxide s. A. G. Polkovnikova, N. S. Usacheva, and A. E. Folomeeva, Khim. Prom. 49, 325 (1973) C. A. 79, 31412 2-ethylenealcohols preferably with Li-di-n-propylamide or Li-di-n-butylamide s. C. L. Kissel and B. Rickborn, J. Org. Chem. 37, 2060 (1972) by thermal rearrangement without added acids or bases s. R. J. Anderson et al., Am. Soc. 94, 5379 (1972) basic rearrangements of oxido compds., review s. V. N. Yandovskii and B. A. Ershov, Russ. Chem. Rev. 41, 403 (1972) (Eng. transl.). 

Polyether Polyols. Polyether polyols are addition products derived from cyclic ethers (Table 4). The alkylene oxide polymerization is usually initiated by alkali hydroxides, especially potassium hydroxide. In the base-catalyzed polymerization of propylene oxide, some rearrangement occurs to give allyl alcohol. Further reaction of allyl alcohol with propylene oxide produces a monofunctional alcohol. Therefore, polyether polyols derived from propylene oxide are not truly difunctional. By using zinc hexacyano cobaltate as catalyst, a more difunctional polyol is obtained (20). Olin has introduced the difunctional polyether polyols under the trade name POLY-L. Trichlorobutylene oxide-derived polyether polyols are useful as reactive fire retardants. Poly(tetramethylene glycol) (PTMG) is produced in the acid-catalyzed homopolymerization of tetrahydrofuran. Copolymers derived from tetrahydrofiiran and ethylene oxide are also produced. 

Another reaction that has received continuing attention is the formation of 77-allyl Pd(II) complexes from allylic alcohols, chlorides, and ethers. In pure allyl alcohol, PdCl2 catalyzes the disproportionation of allyl alcohol to propylene and a product [C6H10O2] which results from oxidative dimerization of allyl alcohol (79) ... 

Derivation (1) Oxidation of allyl alcohol or propylene (2) by heating glycerol with magnesium sulfate (3) from propylene with bismuth-phosphorus-mo-lybdenum catalyst. 

ARCO Chemical uses a technology licensed from Kuraray of Japan to produce 1,4 butanediol from propylene oxide. The propylene oxide is converted to allyl alcohol by isomerization, then further reacted to 1,4 butanediol by hydroformylation of the alcohol with synthesis gas. The hydroformylation is followed by hydrogenation to produce 1,4 butanediol. 

Chemicars propylene oxide business, because allyl alcohol is easily isomer-ized from propylene oxide and provides an alternate market for propylene oxide. 

Acrolein 9- kro-le-9n [ISV acr- (fr. L acr, acer) - - L o/ere] (1857) (propenal, acrylic or allyl aldehyde) n. CH2=CHCHO. A liquid derived from the oxidation of allyl alcohol or propylene, used as an intermediate in the production of polyester resins and polyurethanes. It is an unsaturated liquid aldehyde with a bp of 52° C. It possesses a very pungent odor, and has strong lachrymatory properties. 

Co-adsorption experiments show a complex role of the nature and concentration of chemisorbed ammonia species. Ammonia is not only one of the reactants for the synthesis of acrylonitrile, but also reaction with Br()>nsted sites inhibits their reactivity. In particular, IR experiments show that two pathways of reaction are possible from chemisorbed propylene (i) to acetone via isopropoxylate intermediate or (ii) to acrolein via allyl alcoholate intermediate. The first reaction occurs preferentially at lower temperatures and in the presence of hydroxyl groups. When their reactivity is blocked by the faster reaction with ammonia, the second pathway of reaction becomes preferential. The first pathway of reaction is responsible for a degradative pathway, because acetone further transform to an acetate species with carbon chain breakage. Ammonia as NH4 reacts faster with acrylate species (formed by transformation of the acrolein intermediate) to give an acrylamide intermediate. At higher temperatures the amide may be transformed to acrylonitrile, but when Brreform ammonia and free, weakly bonded, acrylic acid. The latter easily decarboxylate forming carbon oxides. 

In most cases the catalytically active metal complex moiety is attached to a polymer carrying tertiary phosphine units. Such phosphinated polymers can be prepared from well-known water soluble polymers such as poly(ethyleneimine), poly(acryhc acid) [90,91] or polyethers [92] (see also Chapter 2). The solubility of these catalysts is often pH-dependent [90,91,93] so they can be separated from the reaction mixture by proper manipulation of the pH. Some polymers, such as the poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers, have inverse temperature dependent solubihty in water and retain this property after functionahzation with PPh2 and subsequent complexation with rhodium(I). The effect of temperature was demonstrated in the hydrogenation of aqueous allyl alcohol, which proceeded rapidly at 0 °C but stopped completely at 40 °C at which temperature the catalyst precipitated hydrogenation resumed by coohng the solution to 0 °C [92]. Such smart catalysts may have special value in regulating the rate of strongly exothermic catalytic reactions. 

When the commodity chemical propylene oxide is heated to high temperature in the gas phase in a shock tube, unimolecular rearrangement reactions occur that generate the CsHgO isomers allyl alcohol, methyl vinyl edier, propanal, and acetone (Figure 15.9). Dubnikova and Lifshitz carried out a series of calculations to determine the mechanistic pathway(s) for each isomerization, with comparison of activation parameters to those determined from Arrhenius fits to experimental rate data to validate the theoretical protocol. 

Oxidation of the allylic carbon of alkenes may lead to allylic alcohols and derivatives or a, 3-unsaturated carbonyl compounds. Selenium dioxide is the reagent of choice to carry out the former transformation. In the latter process, which is more difficult to accomplish, Cr(VI) compounds are usually applied. In certain cases, mixture of products of both types of oxidation, as well as isomeric compounds resulting from allylic rearrangement, may be formed. Oxidation of 2-alkenes to the corresponding cc,p-unsaturated carboxylic acids, particularly the oxidation of propylene to acrolein and acrylic acid, as well as ammoxidation to acrylonitrile, has commercial importance (see Sections 9.5.2 and 9.5.3). 

Polyether Polyols. Polyether polyols are addition products derived from cyclic ethers (Table 1). The alky lens oxide polymerization is usually initiated by alkali hydroxides, especially potassium hydroxide. In the base-catalyzed polymerization of propylene oxide, some rearrangement occurs to give allyl alcohol. 

Derivation (1) By-product of soap manufacture (2) from propylene and chlorine to form allyl chloride, which is converted to the dichlorohydrin with hypo-chlorous acid this is then saponified to glycerol with caustic solution (3) isomerization of propylene oxide to allyl alcohol, which is reacted with peracetic acid, (the resulting glycidol is hydrolyzed to glycerol) (4) hydrogenation of carbohydrates with nickel catalyst (5) from acrolein and hydrogen peroxide. 

To minimize hydrolysis of the propylene oxide (b.p. 34.2°C) as it is formed, it is flashed (rapidly removed) from the reactive lime slurry. Yields of propylene oxide are 75% or better based on propylene. The advantage of the chlorohydrin route to propylene oxide over the two hydroperoxidation processes is that it yields essentially a single product to market. The disadvantage is the large quantities of coproduced aqueous calcium chloride that has to be discarded safely. The small amount of by-product 1,2-dichloropropane may be pyrolyzed to allyl chloride, useful for the preparation of allyl monomers, allyl alcohol, and allylamines. Or it may be blended with 1,3-dichloropropene to produce an effective soil fumigant. 

Next, we performed experimental testing of TIC s on the following hquids carbon disulfide, acrylonitrile, acrolein, nitric acid, propylene oxide, allyl alcohol, and phosphoras trichloride. The measurements were taken in vials containing three milliliters of hquid. Five spectra from 1100 to 2300 mn were taken of each liquid with 200 scans per spectra. The gain setting was two. The first derivative spectral graph for all of the liquids is shown in Figure 3. 

Scheme 9. Results of isotopic experiments using I,l-

Allyl alcohol can be made by the isomerization of propylene oxide. ARCO Chemical has obtained an exclusive worldwide license from Kuraray in Osaka, Japan for their hydroformulation technology to produce 1,4-butanediol from allyl alcohol. In 1990, ARCO commissioned both the alcohol and the 1,4-butanediol process at their Channelview, Texas propylene oxide plant [91. 1,4-Butanediol is a versatile chemical intermediate that can be used to produce tetrahydrofuran, polybutylene teraphthalate resins, polyurethanes, and pyrrolidone. At this time only a relatively small quantity of propylene oxide is used for this purpose. However, it is growing... 

ARCO Chemical has commercialized a process in their Channelview, Texas propylene oxide complex to produce 1,4 butanediol from allyl alcohol. The technology is licensed from Kuraray of Japan. It fits well with ARCO... 

There are also examples of gas-phase oxidation of allyl alcohol using Pd-Cu or Pd-Ag catalysts (Eq. (8.15)) [48]. The protocol was part of a multistep propylene-oxidation process, and the allyl alcohol starting material was produced from Pd-catalyzed acetoxylation of propylene followed by hydrolysis of allyl acetate (cf. Eqs. (8.2) and (8.3)) [48]. The presence of water improves the conversion of alcohol to acrylic products. 

An alternative route to generate 1,4-butanediol is via the hydroformylation of allyl alcohol. This method was commercialized by LyondellBasell Industries and Dairen Chemical Corporation. Allyl alcohol is produced to isomerize propylene oxide derived from propylene over a lithium phosphate catalyst. Hydroformylation is performed to form 4-hydroxybutyraldehyde (Eq. (10.6)) followed by hydrogenation using Raney Ni catalyst to form 1,4-butanediol (Eq. (10.7)). The patent of Dairen Chemical showed 93% allyl alcohol conversion and 67% 1,4-butanediol selectivity and 31% 2-methyl-propanediol selectivity [7aj. 

Direct air epoxidation of propylene to propylene oxide suffers from selectivity problems. Epoxidation by alkyl hydroperoxide, as practiced by Arco, is based on the use of Mo(CO)g as a homogeneous catalyst. The most impressive use of homogeneous catalysis in epoxidation, however, is in the Sharpless asymmetric oxidation of allylic alcohols. In view of its importance, this enantioselective reaction is included in Chapter 9 which is devoted mainly to asymmetric catalysis. 

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