Fischer Tropsch-type reactions

Chemical reactions similar to the Fischer-Tropsch synthesis have been discussed for some years in connection with prebiotic chemistry they are described as Fischer-Tropsch type reactions (FTT). In its technically optimized form, the FIT 

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Our work on the bifunctional activation of CO insertion was prompted by the thought that strong molecular Lewis acids should be more effective and more general than simple cations. It already had been observed that molecular Lewis acids would promote a molecular Fischer-Tropsch type reaction (5), and that iron diene complexes can be converted to polycyclic ketones by the action of aluminum halides, equation 7,(18), but information on the course of these reactions was sketchy. 

Dr. Anderson. Part of the hydrocarbons in petroleum could have been formed by a Fischer-Tropsch type reaction at say 200°C., at a different place from that in which the petroleum, which contains porphyrins and other thermally labile compounds, is currently found. The broadest interpretation of the similarity between isomers in petroleum and in the Fischer-Tropsch synthesis is that this result suggests that petroleum is produced by radical reactions rather than carbonium ion mechanisms. 

The main byproduct forming reactions in the BASF and Monsanto processes are different. In the former it is the liquid phase Fischer-Tropsch-type reaction, that leads to the formation of products such as such as alkyl acetates, methane etc. In the Monsanto process it is the homogeneous water-gas shift reaction that produces C02 and H2 as byproducts. Also note that the Monsanto process is superior in terms of selectivity, metal usage and operating conditions. 

A nucleophilic attack by 4.7 on CH3I produces 4.8 and I. Conversion of 4.8 to 4.9 is an example of a carbonyl insertion into a metal alkyl bond. Another CO group adds onto the 16-electron species 4.9 to give 4.10, which in turn reacts with I to eliminate acetyl iodide. Formation of acetic acid and recycling of water occur by reactions already discussed for the rhodium cycle. Apart from these basic reactions there are a few other reactions that lead to product and by-product formations. As shown in Fig. 4.4, both 4.9 and 4.10 react with water to give acetic acid. The hydrido cobalt carbonyl 4.11 produced in these reactions catalyzes Fischer-Tropsch-type reactions and the formation of byproducts. Reactions 4.6 and 4.7 ensure that there is equilibrium between 4.7 and 4.11. 

The formation of ethylene by an alkylidene carbene rearrangement,as observed by Caulton [47], might also be a very significant pathway in Fischer-Tropsch-type reactions under homogeneous conditions. 

The organic material in carbonaceous chondrites is of more direct interest with regard to the problem of the origin of life on the Earth, not only because of the possible participation of similar material in the formation of the Earth, but because of the possibility that the mechanisms of formation of terrestrial and meteoritic organic compounds may be related. It has been suggested by Anders et al. (1974) that many of the organic compounds in meteorites may have been formed by Fischer—Tropsch-type reactions. There is reasonable agreement, for example, between certain hydrocarbon isomers... 

Fischer Tropsch-type reactions have also been reported to synthesize... 

McCollom, T.M. Ritter. G. Simoneit, B.R.T. Lipid synthesis under hydrothermal conditions by Fischer-Tropsch-type reactions. Orig. Life Evol. Biosph. 1999, 29, 153-166. 

Two novel routes to triethylborane have been reported. Irradiation of bromoethane and aluminium powder with ultrasound gives ethyl aluminium sesquibromide which on treatment with triethoxyborane gives triethylborane in good yields and a laser initiated gas phase reaction between diborane and ethene gives yields of upto 91%. Allylic boranes have been prepared from allylpotassiiim derivatives and chloroboranes. Hydrolysis leads to the Isomerised olefin and the technique has been used to transform (+)-a-pinene into (+)-3-pinene. Condensation reactions between allylboranes and acetylenes have been developed into a convenient method for the synthesis of bicyclo[3.3.l]nonane derivatives. Mainly linear alkyl derivatives of 9-BBN have been synthesised from the, reaction of iron carbonyls and the organoborane in a Fischer-Tropsch type reaction. ... 

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