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Tungsten carbenes in olefin polymerisation and metathesis
299 Reinvestigation of the Synthesis Higher Aliphatic Alcohols
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The finding that methanol, containing about 10% of aliphatic alcohols, could be admixed to gasoline or fully substitute it has inititated the reinvestigation of the alreadywell-knowndirect synthesis of aliphatic alcohols from CO and H2. For example, Sugier and Freund (IFP) have disclosed in their French patent application (2,369,234 (1978)) that catalysts composed of CI_J~CO-C~~O~-K~O can transform CO,CO2 and H at 250°C and 120 bar to a mix z ure of methanol and higher aliphatic alcohols. Also, Hardman and Beach (Standard Oil Camp., US patent application 905703 (1978)) have developed a series of Cu-Pd-Th02-Na20 catalysts which are active at 2880C and 51 bar in the synthesis of methanol and higher aliphatic alcohols More recently, SUd-Chemie A.G.(Munich) have revealed in their German patent application (OS DE 3005 551 (1981)) that an alkalized Cu-ZnO-A1203 catalyst promoted by Cr,Th,Mn,Ce or La can be applied at 3OOo-350°C and 100 bar for the synthesis of methanol containing lo-30% higher aliphatic alcohols. Recently Snamprogetti (Milan) have disclosed in two German patent applications (OS DE 31 19 290 (1982) and 31 36 088 (1982)) a process (410°C, 260 bar) and catalysts (ZnO-Cr203-K 0) for the production of higher aliph P tic alcohols. These research activities indicate an industrial interest in the potential realisation of this process.
Ammonia
Synthesis
from CO, H70 and N2
Prof. A. Ozaki and his coworkers (Tokyo Institute of Technology) have reported that NH3 is formed from CO, H20 and N2 at a steady rate over Ru-MgO-Cs20, without the formation of any hydrocarbons, at atmospheric pressure and in the temperature range 370°-430°C (Chem.Soc.Japan, Chem.Lett., (1981), 1463). The rate of the reaction was proportional to the pressure of N2, increased with the pressure of H20 but had a maximum at a pressure of about 5 Torr of CO at 405OC. Normal isotope effects were observed in both the synthesis and water-gas shift reactions
Tungsten Carbenes in Olefin Polymerisation and Metathesis R.H. Chandler Ltd (PO Box 55, Braintree, Essex CM7 6HD, UK) have published a review with this title as a supplement to their publications, "Organometallic Compounds" and "Catalysts in Chemistry". The review traces the development of academic interest in tungsten carbenes as catalysts for these reactions and gives details of recent patents to Phillips Petroleum Company (US 4,244,417; 4,248,738; 4,269,780 and also G.B. 2,064,354). The general formula for the catalyst claimed by Phillips is for a neutral, i.e. nonionic, carbene: R \/
Y - (R')m
M (L)n(L’)p Styrene
and Hydrogen
from Ethylbenzene
Prof. S. Teranishi and his coworker S (Osaka University) have found that Mo03/MgO catalysts, even without promoters, exhibit remarkably high activity, selectivity and resistance to sulphur-containing impurities in the catalytic conversion of ethyl-benzene into styrene and hydrogen. The relationship between the surface structure and catalytic activity of the Mo03/MgO catalysts were also studied bv XPS and the dehydrogenation studies have been extended to other paraffins (Chem.Soc. Japan, Chem.Lett., (1981), 1173).
where R is an aryl or substituted aryl radical; R' an alkyl or aryl radical; Y is O,Se,S,N or P; m is 1.0 when Y is 0,Se or Se and 2.0 when Y is N or P; M is W or Re or other metals; L and L' are lioands of specified types; D is 0.0 or-l.0 and when p = 0.b; n-is 5.0 and when p is 1.0, n is 2.0. For reasons of ease of preparation and reactivity, the currently most preferred complex is:
'gH5,
,' - CH3 Ire W(CO)5
of
The finding that methanol, containing about 10% of aliphatic alcohols, could be admixed to gasoline or fully substitute it has inititated the reinvestigation of the alreadywell-knowndirect synthesis of aliphatic alcohols from CO and H2. For example, Sugier and Freund (IFP) have disclosed in their French patent application (2,369,234 (1978)) that catalysts composed of CI_J~CO-C~~O~-K~O can transform CO,CO2 and H at 250°C and 120 bar to a mix z ure of methanol and higher aliphatic alcohols. Also, Hardman and Beach (Standard Oil Camp., US patent application 905703 (1978)) have developed a series of Cu-Pd-Th02-Na20 catalysts which are active at 2880C and 51 bar in the synthesis of methanol and higher aliphatic alcohols More recently, SUd-Chemie A.G.(Munich) have revealed in their German patent application (OS DE 3005 551 (1981)) that an alkalized Cu-ZnO-A1203 catalyst promoted by Cr,Th,Mn,Ce or La can be applied at 3OOo-350°C and 100 bar for the synthesis of methanol containing lo-30% higher aliphatic alcohols. Recently Snamprogetti (Milan) have disclosed in two German patent applications (OS DE 31 19 290 (1982) and 31 36 088 (1982)) a process (410°C, 260 bar) and catalysts (ZnO-Cr203-K 0) for the production of higher aliph P tic alcohols. These research activities indicate an industrial interest in the potential realisation of this process.
Ammonia
Synthesis
from CO, H70 and N2
Prof. A. Ozaki and his coworkers (Tokyo Institute of Technology) have reported that NH3 is formed from CO, H20 and N2 at a steady rate over Ru-MgO-Cs20, without the formation of any hydrocarbons, at atmospheric pressure and in the temperature range 370°-430°C (Chem.Soc.Japan, Chem.Lett., (1981), 1463). The rate of the reaction was proportional to the pressure of N2, increased with the pressure of H20 but had a maximum at a pressure of about 5 Torr of CO at 405OC. Normal isotope effects were observed in both the synthesis and water-gas shift reactions
Tungsten Carbenes in Olefin Polymerisation and Metathesis R.H. Chandler Ltd (PO Box 55, Braintree, Essex CM7 6HD, UK) have published a review with this title as a supplement to their publications, "Organometallic Compounds" and "Catalysts in Chemistry". The review traces the development of academic interest in tungsten carbenes as catalysts for these reactions and gives details of recent patents to Phillips Petroleum Company (US 4,244,417; 4,248,738; 4,269,780 and also G.B. 2,064,354). The general formula for the catalyst claimed by Phillips is for a neutral, i.e. nonionic, carbene: R \/
Y - (R')m
M (L)n(L’)p Styrene
and Hydrogen
from Ethylbenzene
Prof. S. Teranishi and his coworker S (Osaka University) have found that Mo03/MgO catalysts, even without promoters, exhibit remarkably high activity, selectivity and resistance to sulphur-containing impurities in the catalytic conversion of ethyl-benzene into styrene and hydrogen. The relationship between the surface structure and catalytic activity of the Mo03/MgO catalysts were also studied bv XPS and the dehydrogenation studies have been extended to other paraffins (Chem.Soc. Japan, Chem.Lett., (1981), 1173).
where R is an aryl or substituted aryl radical; R' an alkyl or aryl radical; Y is O,Se,S,N or P; m is 1.0 when Y is 0,Se or Se and 2.0 when Y is N or P; M is W or Re or other metals; L and L' are lioands of specified types; D is 0.0 or-l.0 and when p = 0.b; n-is 5.0 and when p is 1.0, n is 2.0. For reasons of ease of preparation and reactivity, the currently most preferred complex is:
'gH5,
,' - CH3 Ire W(CO)5