2-octanol process scheme

Layered-type structure, 92-100 Lewis acidity, 15 Liquid - liquid extraction collective, 276-277 counter-current scheme, 272 equipment, 273 extractants, 279-281 mechanism, 274-276 multistage counter-current, 271 multistage cross-current, 270 one-stage process, 270 principals, 267-269 process performance, 282-283 process schemes, 277,278, selective, 277-278 with 2-octanol, 284-291... 

Scheme 2 Two industrial processes involving a palladium-catalyzed telomerization step the production of 1-octanol by Kuraray (left) and 1-octene by Dow Chemical (right)...

Apart from the oxo process, a series of other reactions are carried out industrially, even if on a smaller scale. Kuraray carries out the hydrodimerization of butadiene and water to produce n-octanol (or 1,9-nonanediol) on a scale of about 5000 metric tons per year [55]. Applications which are significantly smaller up to now are, for example, the production of vitamin precursors by Rh6ne-Poulenc (cf. Scheme 2, [56]) and the production of substituted phenylacetic acids by carbonylation (Scheme 3) [57]) or of biaryls by Suzuki cross coupling (Scheme 4), both by Hoechst AG (now Clariant AG, [57,58]). 

The use of secondary alcohols as reductants for DODH was first reported by Elhnan, Bergman, and coworkers, who employed Re-carbonyl compounds, e.g., Re2(CO)io, as pre-catalysts under aerobic conditions (Scheme 16) [36]. Optimized conditions used the glycol substrate with the mono-alcohol as the solvent, e.g., 3-octanol, at 150-175°C, with 1-2.5 mol% Re2(CO)io and TsOH as a co-catalyst (2-5 mol%). Good yields of the olefin (50-84%) were obtained with representative glycols. The sy -3,4-decanediol was converted highly selectively to trans-3-decene, implicating a sy -eUmination process in the diol to olefin conversion (Scheme 17). Erythritol was converted moderately efficiently to 2,5-dihydrofuran (62% yield), presumably the result of initial 1,4-diol dehydration followed by DODH of the THF-diol intermediate. The nature of the active catalyst was unknown at the time, but was speculated to be an oxidized Re species. 

Telomerization of 1,4-butadiene with water, alcohols, amines, and acids is an extremely useful reaction since it leads to the formation of practically important products. (179,180). For example, the telomer with water, 2,7-octadiene-l-ol can be further hydrogenated to 1-octanol which is a raw material for plasticizers for poly(vinyl chloride). In fact, this reaction was among the processes disclosed in the first patents on the use of TPPTS in biphasic solvent mixtures (58). The catalyst for such telomerizations usually consists of palladium(O) and an excess of TPPTS, TPPMS, or other water-soluble phosphines (eg, with quaternary ammonium substituents). The telomerization of 1,4-butadiene with water was developed into an industrial process by Kuraray Ind. (Scheme 26). Interestingly, the best ligand was the phosphonium salt shown in (Scheme 26) and the catalyst could be prepared in situ from this ligand and [Pd(OAc)2] (179). It is assumed that under the reaction conditions the corresponding tertiary phosphine can be formed to some extent and coordinates to palladium. In any case with a large excess of... 

As for other bicyclic compounds, the resolution of a few bicyclo[3.3.0]octanols [234,235] proceeds with high stereoselectivity. By an efficient enzymatic process, a similar bicyclic structure can be obtained optically pure as a chiral intermediate for the synthesis of [Pg.441]

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