Allylic alcohol from -2,3-butanediol

Both homogeneous and heterogeneous procedures have been developed for the synthesis of allyl acetate from propene (equation 137 and Table 6). Allyl acetate is an interesting intermediate which can be hydrolyzed to allyl alcohol,424 or hydroformylated to a 1,4-butanediol or THF precursor.425... 

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 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. 

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... 

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. 

Allylic alcohols are versatile substrates for hydroformylation. Hydroformylation of allyl alcohol typically favors the linear regioisomer, and this reaction formed the basis of a route to manufacture 1,4-butanediol [15]. Landis recently reported the use of a chiral diazaphospholane for the asymmetric hydroformylation of aUyl silyl ethers [16]. The TBDMS aUyl ether, formed from reaction of allyl alcohol with TBDMSCl, was hydroformylated in 96%ee and 2 1 branched/linear to give the Roche aldehyde (12) which is a widely used chiral building block. High molar substrate/catalyst ratios (10,000 1) and low syngas pressures (15 psi) make this reaction potentially attractive for commercial development. 

---