Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
  • C07C51/145—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide with simultaneous oxidation

Definitions

• ABSIRACT 'An improved method for the oxycarbonylation of olefins to form a,B-unsaturated carboxylic acids, which method employs a catalyst system consisting essen-' tially of certain combinations of compounds of metals of the fourth to seventh sub-groups of the Periodic System with compounds of copper, zinc, cerium, tin, iron, cobalt, and nickel.
• the present invention relates to a process for the preparation of a,,B-unsaturated carboxylic acids by the oxidative carbonylation of olefins in the presence of catalyst systems consiting essentially of certain combinations of compounds of metals of the fourth to seventh sub-groups of the Periodic System with compounds of copper, zinc, cerium, tin, iron, cobalt, and nickel.
• catalyst systems according to the present invention are superior to catalysts comprising a platinum metal, particularly from the point of view of lene, butylene, isobutylene, pentene-2, hexene-l, and
• the heart of the invention in this process is the use of a catalyst system comprising at least one. compound selected from the group consisting of (a) compounds of aluminum, boron, or of the alkaline earth metals and (b) compounds of elements of the fourth to seventh subgroups of the Periodic System, said compounds being soluble in the liquid reaction medium.
• the present invention concerns an improvement in this earlier process in which the oxycarbonylation of olefins is carried out in the presence of a catalyst which, on the one hand, comprises a compound of one of the elements of the fourth to seventh subgroups of the Periodic System and, on the other hand, of at least one compound of copper, tin, cerium, iron, cobalt, nickel, or zinc.
• a catalyst which, on the one hand, comprises a compound of one of the elements of the fourth to seventh subgroups of the Periodic System and, on the other hand, of at least one compound of copper, tin, cerium, iron, cobalt, nickel, or zinc.
• catalyst systerns comprising a compound of rhenium in combination with compounds of copper, iron, tin, cerium, and zinc areoutside the scope of the present invention.
• reaction takes place in a substantially non-aqueous liqoxycarbonylation of olefins in the presence of the catalyst according to the present invention takes place at normal pressure.
• the process can be carried out discontinuously or continuously.
• Oxygen is preferably introduced so that the oxygen content of the gases being removed remains under the explosion concentration, i.e., less than about 10 volume percent, and preferably less than about 3 volume percent.
• the excess gas principally comprising olefin and carbon monoxide, can be reintroduced into the liquid reaction medium.
• the addition of an inert gas, for example nitrogen, is suitable for the avoidance of explosive gas mixtures.
• the amount of catalyst to be employed can vary over wide limits, depending on the specific activity of the catalyst and of the other reaction conditions, and can,
• the mol ratio of the metal from the fourth to seventh subgroups of the j Periodic System to the metal or metals used therewith may vary broadly between :1 and 1:100 since the components exert an almost equivalent catalytic effect.
• aliphatic carboxylic acids such as acetic acid, propionic acid, or crotonic acid are employed.
• Other suitable organic liquids are formamide, monoand dimethyl formamide, acetamide, N-substituted acetamides, acetone, methyl ethyl ketone, cyclohexanone, dimethyl carbon ate, methyl forrnate, diethyl oxylate, of which the less polar liquids are used primarily in admixture with more strongly polar liquids, particularly when the metal compounds are particularly strongly polar.
• organic liquids such as acetyl acetone, dimethyl formamide, dimethyl sulfoxide, or hexamethyl phosphoryl triamide themselves exert a complexing action and can detrimentally affect the course of the reaction, for which reason their suitability must be carefully checked in each individual case.
• the liquid reaction medium is advantageously so selected that it can be easily separated in particular by distillation from the a,B-unsaturated carboxylic acid formed. Therefore, low-boiling liquids are preferably used for the production of high-boiling carboxylic acids, and vice versa.
• the acid which is to be produced can itself be used as reaction medium, thereby avoiding all problems as to separation, i.e., acrylic acid for the oxycarbonylation of ethylene, or methacrylic acid for the oxycarbonylation of propylene.
• the metal compounds used as catalyst should, as mentioned above, be at least of limited solubility in the reaction medium. However, they can also pass into solution by chemical reaction; for instance metal oxides or hydroxides which pass into the corresponding acetates in acetic acid can be employed. It is sufficient for a catalytically active quantity of the metal compounds to pass in solution at the reaction temperature, possibly merely in the presence of all other reactants, while the solubility at room temperature in the pure organic liquid may be any desired. If the active catalyst is not present in dissolved form in the reaction mixture, it must at least form from the dissolved components.
• Suitable metal compounds are, for instance, the chlorides, bromides, chlorates, nitrates, carbonates, cyanides, hydroxides, oxides, formates, acetates, benzoates, phthalates, picrates, acetyl acetonates, etc. Salts free of water of crystallization are preferred in principle.
• the carbonyls and complexing agents of the metals can also be used provided that the complexes are not more stable than the catalytically active complexes.
• Organometallic compounds can also be used in many cases, although they are not preferred because of their high price. It may be advantageous to contact the metal compounds for a prolonged time with the reaction medium and possibly heat them before the start of the reaction.
• the catalysts will not be modified for a prolonged time. It has even been observed that the activity and selectivity increase further upon prolonged operation. Nevertheless it is advantageous to replace the catalyst now and then or continuously because of the unavoidable entrance of impurities.
• catalyst systems are obtained which preferably lead to the formation of an a,B-unsaturated carboxylic acid, side reactions can usually not be completely hindered.
• acetoxy carboxylic acids may be formed when the process is carried out in acetic acid or the two isomeric unsaturated carboxylic acids may be formed in the oxycarbonylation of propylene.
• the catalysts of the invention promote direct oxidation of olefins to the corresponding glycol which then, if one operates in a carboxylic acid reaction medium, is completely or in part converted to the corresponding ester.
• the concurrent reactions which occur in the presence of particularly chosen catalysts, namely the oxycarbonylation of ethylene or propylene to an a,B-unsaturated carboxylic acid on the one hand, and the direct oxidation of the olefin to the corresponding glycol on the other hand can result in the formation of glycol monoesters or glycol diesters of the unsaturated carboxylic acid first formed, i.e., to a result which can be highly desirable.
• a catalyst system comprising manganese-III-acetate and copper-lI-chloride has proved particularly useful. Operation under a pressure between and atmospheres and in a temperature region between 100C. and C. permits the oxycarbonylation to proceed smoothly and with a high yield.
• acrylic acid is formed by the reaction in high yield, as is described more in detail in Example 1 herein. The acetoxypropionic acid can be converted to acetic acid and acrylic acid by pyrolysis.
• the metal compounds to be combined with one another according to the invention form multinuclear complexes having olefin molecules, carboxyl groups, and oxygen as ligands.
• those catalysts which comprise a cyanide or a halide, particularly a chloride or a bromide are particularly active.
• the aforementioned halides may likewise be ligands of the postulated complexes.
• at least one of the metal compounds forming part of the catalyst system can be introduced as a halide and/or the halide or the cyanide of a different metal can be introduced into the reaction mixture.
• the contents of the autoclave were worked up by distillation.
• the acrylic acid formed distilled over at a head temperature of 140C.
• the crotonic acid and methacrylic acid were taken off under vacuum at a temperature between 80C. and 100C.
• Thecrotonic acid solidified in'a cooled receiver (m.p. 72C.).
• reaction products formed were analyzed by known methods using gas chromatography, determination of the bromine number, and by taking the lRspecvtrum and the magnetic resonance spectrum.
• EXAMPLE 2 2.5 g of manganese-III-acetate and 2.5 g of copper-H- chloride were dissolved in 400 ml of glacial acetic acid and 50 ml of acetic anhydride with warming. After saturation with propylene, 80 atmospheres of carbon monoxide and 20 atmospheres of oxygen were introduced under pressure and the vessel was heated to 150C. 14.95 grams of crotonic acid and 13.15 grams of ,B-acetoxy-n-butyric acid were formed.
• EXAMPLE 3 2g of manganese dioxide and 2 g of copper chloride were dissolved in 450 ml of acetic acid and 50 ml of acetic anhydride. The mixture was then saturated with propylene. 8O atmospheres of carbon monoxide and 20 atmospheres of oxygen were introduced under pressure 6 and the reaction mixture was heated to 150C. 1.2 g of crotonic acid and 0.3 g of methacrylic acid were formed.
• EXAMPLE 4 The catalyst employed in Example 3 was again dissolved in 450 ml of glacial acetic acid and 50 ml of acetic anhydride and used as in Example 3. Working up gave 163 g of crotonic acid and 0.25 g of methacrylic acid.
• EXAMPLE 5 The catalyst of Examples 3 and 4 was again dissolved in 450 ml of glacial acetic acid and 50 ml of acetic anhydride. Then, .40 atmospheres of ethylene, 40 atmospheres of carbon monoxide, and 20 atmospheres of oxygen were introduced under pressure and heated to 140C. 33.25 g of acrylic acid were formed.
• EXAMPLE 6 2 g of ttmgsten hexachloride and 5 g of copper-II- chloride were dissolved in 300 ml of glacial acetic acid and 25 ml of acetic anhydride. After saturation with propylene, atmospheres of carbon monoxide and 20 atmospheres of oxygen were introduced under pressure and heated to C. 14.2 g of crotonic acid and 0.5 of methacrylic acid were produced.
• EXAMPLE 7 A solution of 2 g of manganese-III-acetate, 2 g of copper acetate, and 5 g of potassium bromide in 490 ml of glacial acetic acid and 10 ml of acetic anhydride was saturated with propylene by the successive introduction thereinto of propylene at a pressure of 10 atmo- EXAMPLE 8 The same procedure as in Example 7, using a catalyst system comprising 1 g of tantalum-V-chloride and 2 g of copper chloride, produced:
• EXAMPLE 9 A catalyst comprising 2.5 g of manganese-IIl-acetate and 2.5 g of tin-lI-chloride was treated according to Example 8. 3.5 g of crotonic acid and small amounts of methacrylic acid were obtained.
• EXAMPLE 10 A catalyst system comprising 2.5 g of manganese-1H- acetate and 2.5 of cerium-IIl-chloride, when employed according to the process of Example 9, gave: 4.7 g of crotonic acid, 1.4 g of fl-acetoxy-n-butyric acid, and small amounts of methacrylic acid.
• EXAMPLE 1 1 In 25 ml of glacial acetic acid, 3 g of acetylacetone, and 2.4 g of ferric chloride were dissolved while stirring 7 and to this solution 1.1. ml of titanium tetrachloride were added. The precipitated orange-red complex of titanium and iron corresponds to the one published in Chem.Ber. Vol 37, pg. 589 (1904).
• EXAMPLE 13 EXAMPLE 14 The same procedure as in Example 12, using 2 g of manganese-III-acetate and 2 g of nickel-Il-brornide as catalyst, yielded 3.0 g of crotonic acid 0.5 g of methacrylic acid, and
• EXAMPLE 15 The reaction was carried out as described in Example 12 using a solution of 2 g of vanadium-V-oxy-tri acetate, 2 g of copper-II-acetate, and 5 g of potassium chloride in 450 ml of glacial acetic acid and ml of acetic anhydride as catalyst and reaction medium.
• Methacrylic acid and crotonic acid were produced in a 1 to 3 ratio.
• reaction is performed at a temperature between about C. and about 200C.
• reaction is performed under a pressure between about 80 atmospheres and about atmospheres and ata temperature between about 100C. and about C.

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Citations (2)

• 1972
  • 1972-09-27 DE DE19722247312 patent/DE2247312A1/de active Pending
• 1973
  • 1973-07-27 IT IT69282/73A patent/IT1046533B/it active
  • 1973-08-28 FR FR7331092A patent/FR2200234B2/fr not_active Expired
  • 1973-09-17 NL NL7312779A patent/NL7312779A/xx not_active Application Discontinuation
  • 1973-09-20 GB GB4425473A patent/GB1426577A/en not_active Expired
  • 1973-09-21 CA CA181,637A patent/CA1005071A/en not_active Expired
  • 1973-09-24 US US399705A patent/US3920736A/en not_active Expired - Lifetime
  • 1973-09-26 JP JP48108331A patent/JPS4970920A/ja active Pending
  • 1973-09-27 BE BE136118A patent/BE805402A/xx unknown

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