Alcohols, from addition monoxide

An indirect method of producing aldehydes and alcohols from carbon monoxide and hydrogen is the oxo-synthesis (originated by Roelen, Ruhrchemie, A.G.), in which aldehydes are produced by addition of carbon monoxide and hydrogen to olefins at relatively low temperatures and high pressures (cobalt as catalyst), according to the equations ... 

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Catalysts having a very acid nature such as metaphosphoric acid, arsenious acid, boric acid, or salts of these acids have been proposed. The addition of copper as such or as the formate serves to promote the reaction.190 Reaction chambers extremely resistant to corrosion must be tised. Catalysts such as zinc arsenite. or zinc or chromium metaphosphatc having a highly acidic nature are claimed to be effective in the formation of organic acids from carbon monoxide and alcohols at temperatures of about 300° C. and a pressure of 200 atmospheres. Even with such acidic catalysts considerable quantities of esters are stated to be formed.101... 

Later, it was found that alkenes underwent reaction with carbon monoxide (CO) and hydrogen (H2) in the presence of dicobalt octacarbonyl [Co2(CO)g] catalysts to produce aldehydes (i.e., the alkene has been hydroformylated). Presumably (Scheme 6.40) the process involves the coordination of the alkene to the metal (with loss of carbon monoxide, CO) followed by transfer of the carbonyl group to the alkene (with carbon cobalt bond formation) and subsequent reduction. As will be noted later (Chapter 9), aldehydes formed this way can be reduced to alcohols. Thus, additional important chemical intermdiates arise from this, the Oxo Reaction. ... 

The addition of alcohols to form the 3-alkoxypropionates is readily carried out with strongly basic catalyst (25). If the alcohol groups are different, ester interchange gives a mixture of products. Anionic polymerization to oligomeric acrylate esters can be obtained with appropriate control of reaction conditions. The 3-aIkoxypropionates can be cleaved in the presence of acid catalysts to generate acrylates (26). Development of transition-metal catalysts for carbonylation of olefins provides routes to both 3-aIkoxypropionates and 3-acryl-oxypropionates (27,28). Hence these are potential intermediates to acrylates from ethylene and carbon monoxide. 

The use of ethyl ethylthiomethyl sulphoxide in this reaction leads to the desired addition products in much better yields (95-97%). These products were then converted into ketene dithioacetal monoxide derivatives 430 by a sequence of reactions (equation 258)505. Reaction of 2-lithio-l,3-dithiane-l-oxide with benzophenone affords a mixture of the diastereoisomeric tertiary alcohols 431 in a ratio which is temperature dependent (cis trans changes from 3 1 at — 78 °C to 1 1 at room temperature)268. 

Organopalladium(n) intermediates generated from halides or triflates by oxidative addition react with carbon monoxide in the presence of alcohols to give carboxylic acids246 or esters.247... 

Some distinctive features of the insertion reactions reported in Table VII can be summarized as follows First, carbon monoxide gives rise by insertion (5, 195a) to acyl bonds which are easily cleaved by water, alcohols, or compounds with mobile hydrogen. The metal is thus easily removed from the organic part and, being eliminated in its reduced state, can undergo a further oxidative addition, leading to a catalytic cycle. Thus, use of CO is very favorable for catalytic reactions. 

For preparative purposes the method of obtaining aldehydes from the primary alcohols is preferable by far, at least in the aliphatic series. The simple aromatic aldehydes can be obtained by alkaline hydrolysis of the arylidene chlorides, R.CHC12, which are produced from the hydrocarbons by substitution with chlorine (technical method for the preparation of benzaldehyde). In addition to these methods the elegant synthesis of Gattermann and Koch should be mentioned here. This synthesis, which proceeds like that of Friedel-Crafts, consists in acting on the aromatic hydrocarbon with carbon monoxide and hydrogen chloride in the presence of aluminium chloride and cuprous chloride. 

Primary alcohol and aldehydes are produced from butene through the Oxo process. The Oxo process involves the addition of carbon monoxide and hydrogen to an alkene under elevated temperature and pressure in the presence of a catalyst. 

The synthesis of succinic acid derivatives, /3-alkoxy esters, and a,j3-unsaturated esters from olefins by palladium catalyzed carbonylation reactions in alcohol have been reported (24, 25, 26, 27), but full experimental details of the syntheses are incomplete and in most cases the yields of yS-alkoxy ester and diester products are low. A similar reaction employing stoichiometric amounts of palladium (II) has also been reported (28). In order to explore the scope of this reaction for the syntheses of yS-alkoxy esters and succinic acid derivatives, representative cyclic and acyclic olefins were carbonylated under these same conditions (Table I). The reactions were carried out in methanol at room temperature using catalytic amounts of palladium (II) chloride and stoichiometric amounts of copper (II) chloride under 2 atm of carbon monoxide. The methoxypalladation reaction of 1-pentene affords a good conversion (55% ) of olefin to methyl 3-methoxyhexanoate, the product of Markov-nikov addition. In the carbonylation of other 1-olefins, f3-methoxy methyl esters were obtained in high yields however, substitution of a methyl group on the double bond reduced the yield of ester markedly. For example, the carbonylation of 2-methyl-l-butene afforded < 10% yield of methyl 3-methyl-3-methoxypentanoate. This suggests that unsubstituted 1-olefins may be preferentially carbonylated in the presence of substituted 1-olefins or internal olefins. The reactivities of the olefins fall in the order RCH =CHo ]> ci -RCH=CHR > trans-RCH =CHR >... 

Apart from reactions where Michael addition terminated the process, Gabriele and co-workers have developed a useful and expedient palladium-catalyzed synthesis of 4-aminofuran-2-one 113 starting from three simple starting components, a propargyl alcohol, a dialkyl amine and carbon monoxide [98] (Scheme 44). 

Ruthenium trichloride hydrate (5 g.), sodium acetylacetonate (7 g.), and methyl alcohol (140 ml.) are placed in the autoclave in that order. Hydrogen (40 atmospheres) and carbon monoxide (120 atmospheres) (i.e., total initial pressures = 160 atmospheres at room temperature) are then added and the reaction mixture heated at 165° for 4 hours. When cold the pressure is released and the crude orange crystalline dodecacarbonyltriruthenium separated by filtration. The mother liquor is evaporated to dryness and any additional product extracted into hot hexane in a Soxhlet apparatus. The combined products are then recrystallized from hot hexane, f Yields vary slightly from preparation to preparation but are usually in the range 50-55% (2.5 g.). (The checker obtained a yield of 3.0 g., 70%.)... 

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