Patent GB-705791-A (GB)
Title: Improvements in the production of functional derivatives of carboxylic acids
IPC: B01J31/20
Filed: 1952-04-18
Abstract: Derivatives of carboxylic acids are made by treating a monoolefinic compound with carbon monoxide and a basic nitrogen compound containing at least one free hydrogen atom and/or an alcohol at elevated temperature and pressure in the presence of a complex heavy metal salt of cobalt carbonyl hydride.  The catalysts preferably contain as cations in addition to the heavy metal e.g. cadmium, zinc, copper or a metal of the iron group, basic nitrogen compounds, especially ammonia or amines, which contain besides the amino group only carbon and hydrogen, e.g. Fe (NH3)6]++, [Fe (NH3)6]+++, [Co (NH 3)6]++, [Ni(NH3)6]++, [Co (NH2 CH2 CH2 NH2)3]++ and [Cd (NH3)2]++. The amine catalysts are made by conventional methods.  Thus a salt of cobalt carbonyl hydride may be reacted with a complex heavy metal salt as obtainable by adding an excess of ammonia to a solution of a heavy metal salt of a mineral or an organic acid or aqueous solutions or suspensions of salts, oxides, or hydroxides of cobalt may be treated with carbon monoxide in the presence of an amine at 50 to 250 DEG C., preferably 100-200 DEG C., and at least 30 atmos., preferably 150-200 atmos, the required carbonyl hydride being obtained by the addition of a solution of a complex heavy metal salt.  The amount of amine should be at least sufficient to combine with the amine of the metal salt and to replace the hydrogen atoms of the cobalt carbonyl hydride.  Air should be excluded.  The ammonia derived catalysts are prepared in a similar fashion (see Group III).  The catalysts may be added preformed or prepared in situ by adding the ingredients for catalyst formation to the reactants.  Olefinic compounds mentioned include ethylene, cyclohexene, styrene, crotyl, allyl or oleyl alcohol, vinyl and 1-butenyl alkyl ethers and analogous ethers derived from cycloaliphatic hydroxy compounds, acrylic and methacrylic esters, unsaturated carboxylic acids (preferably as salts), unsaturated amines and esters of unsaturated alcohols with saturated carboxylic acids.  Mixtures of olefines optionally containing paraffins may be used. Temperatures of 80-180 DEG C. or up to 250 DEG C. are mentioned. Pressures of at least 50 atmos., especially 100-300 atmos, are preferred.  The catalysts may be applied in the dissolved or suspended state or rigidly arranged. Solvents which may be inert, e.g. saturated aliphatic- or aromatic hydrocarbons or those capable of reacting with CO and H2 may be used. Reactive solvents are used with an excess of CO and H2 or in combination with particularly reactive starting materials.  The use of water should substantially be avoided.  Esters of keto carboxylic acids, ketones and acetals may be formed as by-products.  In Examples ethylene and carbon monoxide are reacted with (1) ethanol and anhydrous ammonia in the presence of [Co (NH3)6] [Co(CO)4]2 or [Cd(N(CH3)3)2] [Co(CO)4]2 to yield ethyl propionate, diethyl ketone and propionamide and (3) methanol in the presence of [Fe(NH3)6] [Co(CO)4]2, [Fe(NH2 CH2CH2NH2)3] [Co(CO)4]2, [Fe(NH2(CH2)6NH2) 3 [Co(CO)4]2 or a pyridine iron complex salt of cobalt carbonyl hydride to yield methyl propionate and diethyl ketone and in (2) octylene and carbon monoxide is reacted with ethanol and anhydrous ammonia in the presence of one of the catalysts of (1) to yield octanoic acid amide. The preparation of the catalysts is also described in the Examples.ALSO:Complex heavy metal salts of cobalt carbonyl hydride which contain cations derived from ammonia are described. Representative of cations specified are [Fe (NH3)6]++, [Fe (NH3)6]+++, [Co (NH3)6]++, [Ni (NH3)6]++ and [Cd (NH3)2]++.  They are made by conventional methods.  Thus a salt of cobalt carbonyl hydride may be reacted with a complex heavy metal salt as obtainable by adding an excess of ammonia to a solution of a heavy metal salt of a mineral or organic acid or aqueous solutions or suspensions of salts, oxides, or hydroxides of cobalt may be treated with carbon monoxide in the presence of ammonia at 50 to 250 DEG C., preferably 100-200 DEG C., and at least 30 atmos. preferably 150-200 atmos, the required carbonyl hydride being obtained by the addition of a solution of a complex heavy metal salt.  The amount of ammonia should at least be sufficient to combine with the anion of the metal salt and to replace the hydrogen atoms of the cobalt carbonyl hydride.  Air should be excluded.  The compounds are used as catalysts in the production of carbonylic acid derivatives from olefines c.f. Group IV(b).  In examples the following salts are made by the methods outlined above [Co (NH3)6], [Co(CO)4]2, [Cd (NH3)2], [Co(CO)4]2 and [Fe(NH3)6] [Co(CO)5]2.