Hydroformylation allyl alcohol

Ma.nufa.cture. Most butanediol is manufactured in Reppe plants via hydrogenation of butynediol. Recendy an alternative route involving acetoxyiation of butadiene has come on stream and, more recendy, a route based upon hydroformylation of allyl alcohol. Woddwide butanediol capacity has climbed steadily for many years. In 1990 it was estimated to be 428,000 metric tons (141), as compared to a Htde more than 70,000 metric tons in 1975... 

Selectivity refers to the fraction of raw material alkene that is converted to product aldehyde, but since hydroformylation typically gives both a linear and branched isomer, selectivity also refers to the relative amounts of each. The linear branched (l b) ratio is highly catalyst dependant. One must simultaneously consider whether the proposed catalyst will give the desired l b selectivity and also whether the proposed catalyst is feasible for use with the catalyst/product separation technologies. For example, water extraction of a polar product, such as in the hydroformylation of allyl alcohol to give 4-hydroxybutanal, would not work well with a sodium salt of a sulfonated phosphine since both are water soluble. 

The desired product in the hydroformylation of allyl alcohol is 4-hydroxybutanal. As with other alkenes, hydro formylation gives both a linear and a branched isomer (Equation 2.1). 

Another route to the diol monomer is provided by hydroformylation of allyl alcohol or allyl acetate. Allyl acetate can be produced easily by the palladium-catalyzed oxidation of propylene in the presence of acetic acid in a process similar to commercial vinyl acetate production. Both cobalt-and rhodium-catalyzed hydroformylations have received much attention in recent patent literature (83-86). Hydroformylation with cobalt carbonyl at 140°C and 180-200 atm H2/CO (83) gave a mixture of three aldehydes in 85-99% total yield. 

Allyl alcohol may be a preferred olefin for rhodium hydroformylation routes to 1,4-butanediol. Comparison of allyl acetate and allyl alcohol as... 

Hydrofoil impellers, 16 673—674 Hydroformulation, 13 768 Hydroformylation, 10 598 allyl alcohol, 2 236—237 ionic liquids in, 26 882—885 maleic anhydride, 15 492 metal carbonyls in, 16 72—73 rhodium-catalyzed, 19 647 Hydroformylation reactions, 13 448 Hydrogasification, coal, 13 845 Hydrogel-based drug delivery,... 

The allyl alcohol is purified by distillation and is hydroformylated with syngas in the presence of a rhodium catalyst to give hydroxybutyraldehyde. 

Industrial hydroformylation of allyl alcohol employs [RhH(CO)(PPh3)3] as catalyst (Kuraray see also 4.1.1.4). In an aqueous solution K[Ru(EDTA-H)C1] catalyzed both the water gas shift and hydroformylation under 10 bar CO at 100-130 °C. The major product was y-hydroxybutyraldehyde (35%) but large amounts of y-butyrolactone and dihydroftiran were also produced [151]. 

Silylformylation and hydroformylation reactions figured prominently in Ojima s approach to isoretronecanol and trachelanthamidine [40]. Thus, silylformylation of alkyne 70 proceeded smoothly to produce aldehyde 71 (Scheme 5.26). Reduction and protodesilylation provided allylic alcohol 72, which was protected to give 73. Hydroformylation in the presence of HC(OEt)3 led to a 2 1 mixture of 74 and 75. Deprotection and amide and amidal reduction then provided the target compounds. 

Hydroformylation - [CARBON MONOXIDE] (Vol 5) - [OXO PROCESS] (Vol 17) -of allyl alcohol [ALLYL ALCOHOL AND MONOALLYL DERIVATIVES] (Vol 2) -catalysts for [CATALYSIS] (Vol 5) -C-19 dicarboxylic acids from [DICARBOXYLIC ACIDS] (Vol 8) -of ethylene [ETHYLENE] (Vol 9) -of ethylene [PROPYL ALCOHOLS - N-PROPYLALCOLHOL] (Vol 20) -of maleate and fumarate esters [MALEIC ANHYDRIDE, MALEIC ACID AND FUMARIC ACID] (Vol 15) -phosphine catalyst [PHOSPHORUS COMPOUNDS] (Vol 18) -platinum-group metal catalysts for [PLATINUM-GROUP METALS] (Vol 19) -rhodium catalysis [PLATINUM-GROUP METALS, COMPOUNDS] (Vol 19) -ruthenium cmpds or catalyst [PLATINUM-GROUP METALS, COMPOUNDS] (Vol 19) -use of coordination compounds [COORDINATION COMPOUNDS] (Vol 7)... 

Hydroformylation. Hydroformylation of allyl alcohol is a synthetic route for producing 1.4-bulanediol. a raw material for poly(butylene terephthalate). an engineering plastic. 

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... 

Hydroformylation of 2,6-dimethyl-6-hepten-2-ol produces hydroxycitronellal (equation 12).22 Subjecting allyl alcohol to hydroformylation reaction conditions with HCo(CO>4 yields only propanal, isomerization taking place more rapidly than hydroformylation.2 Phosphine-modified rhodium catalysts will convert allyl alcohol to butane-1,4-diol under mild conditions in the presence of excess phosphine, however (equation 13).5 30 31 When isomerization is blocked, hydroformylation proceeds normally (equation 14). An elegant synthesis of the Prelog-Djerassi lactone has been accomplished starting with the hydroformylation of an allylic alcohol (equation IS).32... 

An alternative route involving acetoxylation of butadiene and has come on stream, and, more recently, a route based upon hydroformylation of allyl alcohol has also been used. Another process, involving chlorination of butadiene, hydrolysis of the dichlorobutene, and hydrogenation of the resulting butenediol, has been practiced. 

ARCO An intermediate for 1,4-butanediol Rhodium catalyst with chelating phosphorus ligand hydroformylation of allyl alcohol followed by hydrogenation of the resultant aldehyde Reaction 5.9... 

Using hydroformylation and other catalytic or stoichiometric reactions, how could the following transformations be achieved in one or more steps (a) Ethylene to 2-methylpentanol (b) butadiene to 1,6-hexanediol (c) allyl alcohol to butane 1,4-dicarboxylic acid (d) allyl alcohol to 4-carboxylic butanal. 

The introduction of rhodium has allowed the development of processes which operate under much milder conditions and lower pressures, are highly selective, and avoid loss of alkene by hydrogenation. Although the catalyst is active at moderate temperature, plants are usually operated at 120°C to give a high n/iso (linear/ branched) ratio. The key to selectivity is the use of triphenylphosphine in large excess which leads to >95% straight chain anti-Markovnikov product. The process is used for the hydroformylation of propene to n-butyraldehyde, allyl alcohol to butanediol, and maleic anhydride to 1,4-butanediol, tetrahydrofuran, and y-butyrolactone. 

Matsumoto and Tamura (at Kuraray Co.) have demonstrated that the combination of simple bis(diphenylphosp-hino)alkane ligands and PPhs has a very positive effect on catalyst stabihty and the reduction of unwanted side reactions. This is most evident in the hydroformylation of a reactive alkene substrate such as allyl alcohol. The use of HRh(CO)(PPh3)2 in the presence of excess PPhs leads to relatively rapid catalyst deactivation to unidentified species. The addition of just over 1 equivalent of dppb, for example, leads to a stable, active hydroformylation catalyst. Use of dppb either by itself, or in quantities higher than 2 equivalents, leads to catalyst deactivation and/or poor activities and selectivities. ARCO Chemical Co. licensed the Kuraray technology to build the first conunercial plant (1990) for the hydroformylation of allyl alcohol to produce 1,4-butanediol (Scheme 11). 

The same catalyst precursor, generated from [(EDTA)RuCI] which is also water soluble, was used for the hydroformylation of allylic alcohol under the same reaction conditions (//). At 50 bar and 130°C, in water as solvent, 4-hydroxybutanal was produced [Eq. (5)], together with about 2% of formaldehyde. However, the reaction proceeded further to give butane-1,4-diol by hydrogenation and y-butyrolactone as well as dihydrofuran by cyclization [Eq. (6)]. The same catalytic cycle as that proposed in Scheme 3 can be considered. A kinetic investigation revealed a first-order dependence on the ruthenium complex concentration and on the allyl alcohol... 

The kinetics of the new commercial process of hydroformylation of allyl alcohol was studied by Chaudhari in the temperature range from 60 to 80 °C [114]. The rate of reaction is first order in catalyst concentration and 1.5th order in hydrogen partial pressure. The dependence on p CO) does not differ from that observed in the hydroformylation of nonfunctionalized olefins. The reaction is retarded at higher substrate concentrations (> 1.25 mol/L). This substrate inhibition is not fully understood on the molecular level. The apparent activation energy for the oxo reaction of allyl alcohol was found to be 94 kJ/mol. 

The kinetics of the above-mentioned biphasic hydroformylation of allyl alcohol (see eq. (6)) were described by the rate eq. (12) [20]... 

An interesting reaction discovered by Wakamatsu involves the cobalt-catalyzed carbonylation of aldehydes in the presence of primary amides to give A-acylamino acids in high yield (equation 26). By combining this reaction with known catalytic routes to aldehydes, for example isomerization of allyl alcohols or hydroformylation of alkenes, it is possible to achieve the direct synthesis of A-acylamino acids from precursors other than aldehydes. ... 

Very efficient asymmetric hydroformylation of alkenes, dienes, and heterocycloalkenes is achieved with a complex formed by mixing RhCacacXCO) and 52. The diphosphines 53 and 54 have found utility in the preparation of y-lactones" from allylic alcohols and 3-substituted cyclopentanones " from 4-substituted 4-pentenals, respectively, and in chiral forms. 

The hydroformylation of the orf/zo-prop-2-enylphenol 81 which contains no benzylic hydroxy group gives a mixture of the open-chain aldehyde 82 and the seven-membered cyclic hemiacetal 83 in a 82 83 ratio of approximately 40 60 (equation 34) °. The ben-zofuran epoxide 85 and its valence-isomeric quinone methide 86, both readily obtainable from benzofuran 84, rearrange thermally above —20°C to form the allylic alcohol 87 and the tautomeric phenol 88 (equation 35) . ... 

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