JPS6013009B2 - Rhodium-catalyzed oxidation method for producing carboxylic acids - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates generally to a method of making carboxylic acids.

More specifically, the present invention relates to a rhodium-catalyzed one-step process for the direct production of carboxylic acids from the corresponding olefins. Carboxylic acids have many uses in the chemical industry.

For example, propionic acid is useful as a grain preservative;
And higher acids are used in the manufacture of detergents. Many different methods are known for producing carboxylic acids, such as hydroformylation of olefins and subsequent oxidation of the resulting aldehyde.

The acid produced has one more carbon number than the olefin. For example, an olefin (eg, ethylene) is hydroformylated by reaction with carbon monoxide and hydrogen to produce the corresponding aldehyde (propiosoaldehyde), which is then oxidized to the corresponding acid (propionic acid). In some cases, after the hydroformylation reaction of olefins with carbon monoxide and hydrogen (also known as the oxo process), the aldehyde is recovered and purified before oxidizing it to acid. Other related methods in the prior art include:
No purification of aldehyde is required.

For example, German Patent No. 2,604,545 hydroformylates the corresponding olefin under high pressure of 100 to 60 ruels and directly oxidizes the resulting aldehyde-containing reaction mixture, and also performs both steps using rhodium. A two-step process for producing alkyl carboxylic acids in the presence of a carbonyl rust catalyst is disclosed. U.S. Patent No. 3,
In the 0.67 series, the allylic ester of a lower paper fatty acid was first hydroformylated in the presence of both a rhodium carbonyl fin catalyst and an inert organic solvent, and then the resulting reaction mixture was directly oxidized in the presence of a lower fatty acid. A method is disclosed for simultaneously obtaining both methacrylic acid and butyrolactone by including a rhodium catalyst and recovering the product after separation of the residue.

U.S. Pat. No. 3,520,937 discloses a technique for treating a cobalt- and aldehyde-containing oxo reaction mixture with an oxidizing agent to provide a cobalt-incompatible material.

The amount of oxygen is said to be insufficient to oxidize the product aldehyde. Yet another follow-up technology method is
It is possible to directly oxidize or carboxylate olefins to produce various compounds.

For example, U.S. Pat. No. 3,384,66 discloses various precious metal ions and nitric acid. A method is disclosed for converting olefins to the corresponding aldehydes or ketones by oxidation with molecular oxygen in the presence of a catalyst comprising an aqueous solution containing either ions of nitrous acid or mixtures thereof. German Pat. A method is disclosed for oxidizing olefinos to, for example, ketones by reacting them in the presence of a phosphite ligand.

US Patent No. 3,818'06 discloses a Group metal catalyzed hydrocarboxylation process for the production of carboxylic acids that involves reacting an olefin with carbon monoxide and water.

The catalyst system comprises an iridium or rhodium containing compound, a halide promoter and a stabilizer consisting of an organic derivative of pentavalent phosphorus, arsenic, antimony, nitrogen or bismuth. This stabilizer is said to prevent precipitation and solids build-up, which usually adversely affect the stability of the catalyst. See also US Pat. No. 3,8104, US Pat. No. 3,810,489, and US Pat. No. 3,944,604. Others, including Mr. Blum, went to Tetrahedron. 38, pages 3665-36 (1967), chlorotris (triphenylphosphine), a rhodium catalyst,
Q monoxidation of alkylbenzenes with rhodium RhC1(PPh3)3 (herein "Ph" niphenyl) is disclosed.

Specifically, the alkylbenzene ethylbenzene is oxidized to acetophenone by air in the presence of a catalyst. Other than Mr. Fushi, Joumal of ○rga
In Mmetamc Chemistry 26 (1971), pages 417-430, a mechanism of cyclohexene oxidation by transition metal bodies is proposed.

Specific results have been given for the oxidation of cyclohexene to cyclohexene oxide, cyclohexanone, and cyclohexanol in the presence of various catalysts including triphenylphosphine and enriched rhodium.
In pages 3,898 to 3,900 of Journal of the Chemical Society of Japan 43(12) (December 1970), Mr. Takao et al. oxidation and the effects of various solvents on the oxidation products.

In non-polar solvents such as toluene, the main products were both acetophenone and penzaldehyde. Also,
Oxidation of methylstyrene with the same catalyst has also been reported. A later report by Mr. Takao et al., Journal of the Chemical Society of Japan 45(5) (May 1972), No. 1,505-1,
On page 507, the oxidation of cinnamaldehyde catalyzed by rhodium in various solvents is reported.

Two rhodium bodies, chlorocarponylbis(triphenylphosphine)rhodium and chlorotris(triphenylphosphine)rhodium, cause catalytic oxidation of cinnamaldehyde in toluene to produce penzaldehyde, glyoxal, benzene and styrene. There was found. Also, Journal of the Chemical Society of Japan 45(7) (
Takao et al. report on the oxidation of vinyl esters in solvents catalyzed by chlorotris(triphenylphosphine)rhodium, in pages 2,003-2,006 of King Jul. 1972.

The type of reaction product obtained is determined in part by the substituents on the olefinic carbon atoms. For example, vinyl acetate was oxidized in toluene to produce acetone, propionaldehyde, and methyl vinyl ether, whereas vinyl propionate yielded methyl ethyl ketone, butyraldehyde, and ethyl vinyl ether. Other than Mr. Dutley, J. C. S. Dalton (1974
), pages 1,926-1,931, disclose the rhodium-promoted oxidation of Q-olefins to methyl ketones in benzene.

Chlorotris (triphenylphosphine) rhodium and carbonylhydridotris (triphenylphosphine)
Two rhodium keys, rhodium, have been shown to catalyze the reaction. Other than Mr. Martha, Joumalof
the American Chemical Society
ty97(7) (April 1975), page 1,96~
On page 1,968, rhodium body R & (CO), 6
catalyzes the oxidative cleavage of C--C bonds in ketones to carboxylic acids.

The particular reaction reported involved suspending rhodium in cyclohexanone as a solvent and pressurizing with oxygen to produce adipic acid. Various other prior art methods disclose hydroformylation processes in which the presence of oxygen retards the reaction. For example, Polyp Riki et al. Petr Mhemial979, 19 (1-2), 5
-12, HRh(CO
) (PPh3) 3 (this) discloses the low-pressure hydroformylation of olefins (1-octene, di- and triisobutylene, allyl alcohol, styrene and dibentene) with "Ph" niphenyl.

The authors disclose that compounds such as oxygen, which is more reactive towards catalysts than alkenes or CO, form stable compounds that retard hydroformylation. Mr. Matthi and others published the Journal of the Chemical Society of Japan 19M. 1 (May 1977), Hido.

We propose a mechanism to explain the deactivation of rhodium rust catalysts used in formylation reactions. The specific catalysts reported are:
Rhodium (as R&CI2(CO)4) is enriched with a triphenylphosphite ligand. The authors concluded that the catalyst loss was primarily due to the oxidation of triphenylphosphite to triphenylphosphate caused by the small amount of oxygen present in the syngas. ．． The prior art also teaches the regeneration of dehosted rhodium rust bodies with oxygen.

For example, Japanese Patent Publication No. 51-23,212 describes a rhodium-catalyzed hydroformylation process, more specifically, in which the deactivated rhodium catalyst is treated with oxygen in a separate step and the regenerated catalyst is then recycled to the hydroformylation reaction. Discloses a technology for regenerating a rhodium catalyst that has become deactivated during the process. Currently pending U.S. Patent No. 7
No. 0313pi (published as Belgian Patent No. 850 542) discloses a hydroformylation process in which deactivated rhodium fin catalysts can be regenerated by introducing catalytic small amounts of oxygen into the hydroformylation reaction system.

The amount of oxygen used is small (i.e., just enough to detoxify and reactivate the catalyst) and substantially all of the oxygen is consumed by the glue gun in the catalyst to liberate the catalytic rhodium, which The catalyst is reactivated. Other prior art discloses hydroformylation processes where oxygen is present.

For example, U.S. Pat. No. 3,920,754 discloses that formyl-
and hydroformylation processes to form hydroformyl-substituted alkene derivatives. U.S. Patent No. 3,954,8
No. 77 is a valent group metal (e.g. rhodium) and pentavalent phosphorus,
A process for olefin hydroformylation using a key with a ligand consisting of an arsenic or antimony compound (eg, phosphine oxide) is disclosed.

U.S. Pat. No. 3,5550 discloses a method for maintaining catalyst activity by treating all or a portion of the recycled reaction medium containing the catalyst with an aqueous alkaline solution to extract the carboxylic acid byproducts that deactivate the catalyst. A noble metal catalyzed hydroformylation reaction is disclosed. This acid is believed to be formed by slight oxidation of the aldehyde product due to oxygen contamination of the reactant gas stream. For many years, all industrial hydroformylation reactions used cobalt carbonyl catalysts that required relatively high pressures (currently on the order of 10 atmospheres or more) to maintain catalyst stability.

Earl El. Mr. Pruitt and J.A. Smith, U.S. Patent No. 3,527,8, issued September 8, 1970.
No. 0y discloses a novel hydroformylation process in which Q-olefins are hydroformylated with carbon monoxide and hydrogen to produce aldehydes in high yields at low temperatures and pressures, where the normal to (or branched) aldehyde isomer ratio is high. This process uses certain rhodium rust catalysts and operates under limited reaction conditions to achieve hydroformylation of olefins. This new process operates at significantly lower pressures than previously required with conventional techniques, resulting in substantial benefits, including lower initial capital investment and lower operating costs. Furthermore, many desirable direct mirror aldehyde isomers could be prepared in high yields. The hydroformylation process described in the Plate and Smith patents mentioned above involves the following essential reaction conditions.

'1} A rhodium catalyst that is a combination of rhodium, carbon monoxide, and a triorgano-adjacent gun.

The term "key body" refers to one or more electron-rich molecules or atoms that can exist independently and one or more electron-poor molecules or atoms (each of which can also exist independently). ) refers to a coordination compound formed by combining with The triorgano-adjacent IJ gund where the iso atom has an available or unshared pair of electrons can be bonded with the rhodium.'2) Vinyl group C&
A Q-olefin source of Q-olefin compounds characterized by a terminal ethylenic carbon-carbon bond such as =CH-. They may be straight-chain or branched and may contain groups or substituents that do not essentially interfere with the hydroformylation reaction, and they may contain more than one ethylenic bond. I can do it. Propylene is an example of a preferred Q-olefin. '3' Triorga/phosphorus ligand such as triarylphosphine.

Desirably, each organic moiety in the ligand has no more than one carbon atom. Triarylphosphines are preferred ligands, one example of which is triphenylphosphine. '41 Concentration of triorganophosphorus ligatodes in the reaction mixture sufficient to provide at least 2, preferably at least 5 moles of free ligand per mole of rhodium metal rusted or bonded to the rhodium atoms or in addition to the ligands. .

{5} About 50 to about 14yo, preferably about 60 to about 12yo
Temperature of 60. {6) Total hydrogen and carbon monoxide pressure below 45 sia, preferably below 35 sia.

[7--Maximum partial pressure of carbon monoxide not more than about 75% based on the total pressure of carbon oxide and hydrogen, preferably less than 50% of this total gas pressure.

In industrial hydroformylation monoxide processes for producing carboxylic acids, the resulting aldehyde is usually recovered and then oxidized to the corresponding acid.

If the oxidation process is carried out without an aldehyde purification step and with a skin group metal catalyst such as a rhodium-based catalyst, the oxidation process can be carried out in the presence of an inert aromatic or aliphatic solvent. Acidic catalyst stability and activity problems are encountered. Hydroformylation of Olefins to AcidsEven without the use of inert solvents in the monooxidation route, conventional techniques involve dividing the process into two steps (i.e., hydroformylation followed by a separate oxidation without purification of the aldehyde). It was necessary to do so. The present invention encompasses a process for producing carboxylic acids directly from olefins by reacting olefins with carbon monoxide, hydrogen and in one step using a stable rhodium-catalyzed catalyst; Stability and activity are maintained through the use of pentavalent Group V ligands in the catalyst. Thus, a catalyst system is provided that is stable under both hydroformylation and oxidation reaction conditions even when placed in an inert organic solvent. The process of the invention allows the production of acids and their anhydrides directly from the corresponding olefins in a single operation using a single stabilized catalyst. Even when this oxidation is carried out in an inert organic solvent, the rhodium rust catalyst is stable. According to the present invention, carboxylic acids having from 3 to about 21 (or more) carbon atoms can be produced. Embodiments of the present invention (hereinafter referred to as the '1 hydroformylation monoxide process' for convenience) involve treating an olefin with carbon monoxide, hydrogen and oxygen in the presence of a rhodium rust catalyst, preferably in an inert organic solvent. It is a one-step process consisting of reacting to produce the corresponding acid having one more carbon atom than the olefin. In this case:
Rhodium rust catalysts contain pentavalent Group V ligands that stabilize the catalyst against deactivation.

In embodiments of the present invention, the exact mechanism for converting olefins to carboxylic acids is not yet known. however,
This embodiment provides a method for converting acids into a single process, as compared to prior art methods that require the production of aldehydes that optionally recover and purify the aldehyde and then oxidize it in a separate step to the corresponding acid. Provides the benefits of manufacturing in process. The so-called hydroformylation monoxide process of the present invention generally involves the addition of a catalytic amount of rhodium enriched with a stabilizing pentavalent Group V ligand at a temperature and pressure sufficient to directly produce the corresponding carboxylic acid. A make-up gas in the liquid reaction medium containing (this is typically olefin, hydrogen,
(including carbon monoxide and oxygen).

Preferably, the reaction is carried out in an inert organic solvent.
The olefins that can be reacted in the one-step hydroformyl-oxidation process of the present invention can be any olefins having from 2 to about 2 carbon atoms and one ethylenic carbon-carbon bond. The olefin may be linear or branched and may contain groups or substituents that do not essentially interfere with the progress of the reaction. Additionally, it is contemplated within the scope of this invention to enhance both Q-olefins as well as internal olefins. Typical Q-olefins include, for example, ethylene, propylene, 1-butene, 1-bentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-deceso, 1-undecene, 1-dodecene and higher. Analogues of . The most preferred Q-olefin is ethylene. Typical internal olefins include, for example, 2-butene, 2-bentene,
2- or 3-hexene "includes 3-decene, 4-decene, 2-undecene, 3-undecene, 3-undecene, 4-undecene, 5-undecene and higher analogs. The reaction temperature is Generally, it may be about 75 to about 200 oo.

Above about 200 qo, the catalyst may become deactivated at moderate operating pressures, whereas below about 75 qo it may be difficult to achieve desired reaction rates. The preferred reaction temperature is about 95 to about 110 degrees. The reaction is carried out at a total gas pressure of about 100 to about 1,00 sia (
(olefins, hydrogen, carbon monoxide and oxygen). The maximum pressure at which the reaction can be carried out is not particularly critical and is in fact limited primarily by economic considerations. Regarding the minimum pressure, it is about 10
Below 0 psia, the reaction rate may be lower, and in addition, rhodium catalysts tend to be less stable. The preferred total gas pressure is about 250 psia to about 35 psia.
It is. As previously stated, the total gas pressure consists of the sum of the partial pressures of oxygen, carbon monoxide, olefins and hydrogen. The respective partial pressures may vary over wide ranges based on the following considerations. Due to stoichiometric requirements, olefins and hydrogen can generally be used in approximately equimolar amounts and therefore their respective partial pressures are approximately equal. The partial pressure of oxygen in the reaction system is somewhat limited by safety considerations. As a result of this, it may not be possible to meet the stoichiometric requirements of the reactions that produce carboxylic acids and their hydrates. In such cases, it may be necessary to periodically supply additional oxygen to the reaction system to ensure an adequate partial pressure of this component. Although increasing the amount of oxygen increases the selectivity of the reaction toward the acid rather than the aldehyde product (i.e., less than about 1 mol % oxygen may provide insufficient selectivity toward the acid), appears to simultaneously retard normal hydroformylation activity. Increasing the ratio of oxygen to hydrogen or oxygen to olefin tends to increase selectivity for carboxylated (ie, acids and anhydrides) products rather than non-carboxylated (ie, aldehydes and ketones) products. Finally, variations in the feed gas ratio do not appear to result in significant changes in the stability of rhodium-containing catalysts, although catalyst stability is significantly lower under oxygen-containing conditions when compared to oxygen-free hydroformylation reaction conditions. Based on the above, the hydroformylation monoxide reaction is generally performed using the oxygen to carbon monoxide to olefin to hydrogen ratios (according to the ideal gas method) of the feedstock or make-up gas exposed to the reaction system. (expressed as volume or mole % of total gas feedstock) from about 1 to 5:30 to 70:5
~35: It can be performed as 5 to 35.

Each range does not necessarily increase to 100%. This is because each component can be adjusted relative to one or more of the other components to achieve the desired result, depending in part on the criteria outlined above. 02 vs CO vs Ole
The preferred gas ratio of fins to Japan 2 is about 2-3:50-60
:20-30 and 20-30, and in the case of the most preferred reaction (ethylene to propionic acid) the gas ratio is approximately 3:50:23:23.

As previously described, the present process is preferably performed in an organic solvent inert to the reaction conditions, preferably with a boiling point at least as high as (but preferably higher than) the boiling point of the carboxylic acid produced. It is carried out in some inert aliphatic or aromatic organic solvent.

Typical paper aliphatic inert solvents include saturated hydrocarbons having from about 9 to about 2 solid carbon atoms, such as nonane, undecane, dodecane, and the like. These saturated hydrocarbons may be straight chain or branched, and more highly branched materials are preferred. Typical inert aromatic solvents include aromatic hydrocarbons such as benzene and biphenyl, and aromatic hydrocarbons substituted with at least one saturated aliphatic hydrocarbon group such as toluene, xylene, and the like. Generally, the saturated aliphatic hydrocarbon substituents in these aromatic solvents can contain from 1 to about 13 carbon atoms, and they can be straight chain or branched. In general,
The type of solvent used is not critical, and the reaction conditions can be adjusted to prevent the solvent from becoming more volatile than the carboxylic acid produced.

Optionally, the inert organic solvent may initially contain from 0.5 to 5% by weight of solvent, based on the total weight of the carboxylic acid to be produced. The amount of acid in the solvent is not particularly critical. This is because, in practice, this is a limitation on how quickly the produced acid is desired to be removed from the reaction system. By having an acid in the reaction medium at the beginning of the reaction, the formation of the anhydride is promoted more than the acid. The amount of solvent used in the practice of this invention is limited only with respect to the catalyst, ie, it must be such that it solubilizes at least a catalytic amount of rhodium. Generally, the solvent is used to provide a concentration of catalytically active rhodium, calculated as free metal, of from about 25 to about 1,20 kg, preferably from about 50 to about 40 kg. Regardless of the amount of solvent or its presence, the catalyst is used in an amount that provides the stated amount of catalytically active rhodium. Pentavalent Group V ligands have the formula or a branched saturated hydrocarbon group (methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-amyl, hexyl, octyl,
decyl, dodecyl), aryl groups (such as phenyl or biphenyl), saturated straight or branched hydrocarbon substituted aryl groups (such as tolyl, xylyl etc.) or aryl substituted straight or branched saturated hydrocarbon groups (such as tolyl, xylyl etc.) phenylmethyl, phenethyl, etc.)].

The number of carbon atoms in each of R, , R2 and R3 is 15
and the total number of carbon atoms in R, R2 and R3 preferably does not exceed 30. Preferred ligands are those in which M is phosphorus and R, , R2 and R3 are 5-8
are the same direct mirror hydrocarbon radicals having 5 carbon atoms. The most preferred ligand is tri(n-octyl)phosphine oxide. Pentavalent Group V ligands can be obtained commercially or made by conventional methods.

For example, the preferred ligand tri(m-octyl)
In the case of phosphine oxide, tri(n-octyl)phosphine is first prepared by methods known in the art and then reacted with an oxidizing agent such as hydrogen peroxide or oxygen;
The resulting phosphine oxide can then be recovered. For example, Mr. Harvey's Joumal of
the ChemicalOSocietsu, Ch.
chemical communications369
(1976). The exact nature of the active rhodium enantiocatalytic species is not known, but it is believed that it consists essentially of rhodium stabilized by a pentavalent Group V ligand.

The expression "consisting essentially of" is meant to include rather than exclude other IJ atoms such as hydrogen and carbon monoxide if they mirror rhodium under the reaction conditions. However, this term is meant to exclude amounts of other substances (such as halides and sulfur) that would poison or deactivate the catalyst. What is known is that the pentavalent V
The fact is that rhodium is a stable catalyst for the production of carboxylic acids from olefins in the presence of a group ligand and the reactants used in the hydroformylation monoxide reaction.
Active rhodium complex catalyst species are free of any rhodium-bonded halogens, such as chlorine and similar species, and are generally stable in hydrogen, carbon monoxide, and possibly liquids that can be used as solvents in the reaction and reaction conditions. It is theorized to contain rhodium metal and a leaded pentavalent ligand to create a stable catalyst underneath. The active species, whatever its exact structure, can be obtained by two different techniques.

The active rhodium fin catalyst precursor can be preformed and added to the hydroformylation monoxide reaction mixture (as is), or the required rhodium fin catalyst precursor components can be introduced directly into the reaction mixture. However, in both cases the active rhodium rust catalyst is formed in situ. Example 20 Preforming an active rhodium rust catalyst precursor in solution by combining a rhodium compound, such as rhodium dicarponylacetylacetonate, and a suitable pentavalent ligand, such as tri(n-octyl)phosphine oxide. can do. This precursor solution can then be added to the hydroformylation monoxide reaction mixture to produce an active rhodium catalyst in situ. Alternatively, the necessary active rhodium catalyst precursor components, i.e., rhodium dicarbonylacetylacetonate or rhodium compounds such as RL(CO), Jun or Rh6(CO),6, and tri(n-octyl)phosphine oxide, The valent ligand (as is) is added to the hydroformylation monoxide reaction mixture. In either case, the active rhodium rust catalyst species are formed in situ and under the conditions present in the reaction medium. The latter technique, ie, forming an active rhodium complex catalyst species by adding a rhodium compound and a ligand to the reaction medium, is preferred. The pentavalent Group V ligand stabilizes the catalyst against deactivation, regardless of its method of formation, and generally contributes approximately 0.0% to the liquid reaction medium, based on the total liquid reaction medium volume.
0.00 molar to about 0.08 molar. The hydroformylation monoxide method of the present invention includes:
As previously described, makeup gas is provided into the liquid reaction medium.
It is usually carried out in the liquid phase by feeding. The liquid reaction medium is preferably freed of high-boiling liquid aldehyde condensation products that may have formed during the reaction by conventional techniques. This is because they may not be inert to the reaction. For example, these and other by-products can sometimes be removed by distillation or extraction. The process can be carried out continuously or batchwise or semi-batchwise. In any case, it is sometimes necessary to recharge the system with catalyst components. Whether it is necessary depends on several factors, including the desired reaction rate, amount of reaction medium, reaction conditions, etc. The catalyst or components thereof can be added to the reaction medium by any suitable technique such as those described above for initial catalyst loading. The carboxylic acid produced can be recovered by any suitable conventional technique, such as by distillation or extraction.

The oxygen-containing gas supplied to the liquid reaction medium is generally
Contains approximately 2-10% oxygen by volume.

Typically, this gas stream consists of pure oxygen diluted with air or nitrogen. Again, the maximum amount of oxygen in the gas stream delivered to the liquid reaction medium is primarily determined by safety considerations, taking into account the reaction temperature and pressure. It has been found that rhodium catalysts are more stable when carbon monoxide is present in the reaction medium in up to equimolar amounts (based on air as oxygen source), and this is therefore preferred.

Conventional techniques, such as those described above, can be used to recover the carboxylic acid product and remove unwanted debris from the reaction medium.

Also, all conventional equipment can be used in embodiments of the invention. In embodiments of the invention, at least one of carboxylic acids and their anhydrides can be produced, ie individually or as a mixture.

Of course, the anhydride can be converted to its acid form by conventional techniques, such as by hydrolysis. The invention is further illustrated by the following examples, some of which represent methods outside the scope of the invention for comparison.

Example 1 3 In the rocker cylinder, the solvent and the ligand are 0.1
Rhodium dicarbonylacetylacetonate Rh
(CO)2AcAc, and 10 si of ethylene and 10
A mixture of 10 psi carbon monoxide and 10 psi hydrogen (total gas pressure 30 psi) was charged at an initial charge temperature of 30-3500 ml.

The system was then heated to 100±3° C. (unless otherwise noted), the rocker started, and the system heated under these conditions for 4.5 to 5 minutes by repressurizing with gas as needed. The mixture was maintained for an hour, cooled to 25°C, degassed, and the liquid contents were removed and analyzed by vapor phase chromatography (VPC) to determine the yield of propionaldehyde.
The conditions and results are shown in Table 1 below. Although these experiments are not within the scope of the present invention, they show that under hydroformylation conditions, as opposed to trivalent Group VA ligands, their pentavalent analogues are more likely to react in the inert solvent toluene than acetophenone. This example shows that it seems to work effectively. Notes to Table 1 * It is difficult for the grains to sink into the Fujishitsuna (or) flowing carp. Ura Ph = Phenyl TOPO
=tri(n-octyl)phosphine oxide Example 2 Solvent (
Except that a total of 500 [
The procedure of Example 1 was repeated.

The materials, conditions and results are shown in Table 2 below. None of these experiments fall within the scope of the present invention, however, they do show the effect that various solvents have on pentavalent phosphine oxide under hydroformylation conditions. Funabune Ji Sankune Fuike Misaki 'Ya S fake Kyousan S ↑ It's a mistake, Sanren Funen Fuku Kiyoshi! 'Takudokoro.

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”” Part A 4 A < Fukon Example 3 Except for using the ligands shown in Table 3 below,
The procedure of Example 1 was followed.

At the completion of the reaction, the amount of rhodium still retained in the liquid reaction medium was determined by atomic absorption and is shown in Table 3 as *Rh%. The conditions and results are shown in Table 3 below. Although none of these experiments fall within the scope of the present invention due to the absence of oxygen, the effect of pentavalent ligands on the stability of rhodium is seen. Table 3 * Same meaning as in Table 2 ** The data are from an experimental form in which approximately 100% Rh was dissolved in solution and recovered. It costs 30 and Kamisagi.

Note: Ph, TOP○ and Et have the same meaning as above. Example 43 In the rocker cylinder, 0.12 hours of rhodium dicarponylacetylacetonate Rh(CO)2A was added.
cAc, toluene (PhCH3) and propionic acid (EtC02H) to give an initial solution volume of 500'
and an IJ gund, and a gas mixture having a total pressure of 30 to 35 capsia as shown in Table 4 below.
It was prepared at a temperature of oo.

The system was then heated to 100±3° C. and the rocker was started. These temperature conditions were maintained for 4.5 hours after which time the locker was cooled to 25-30°C, degassed and the liquid contents removed and analyzed. The yield and distribution of the product was determined by analysis by VPC, and the amount of rhodium retained in solution by atomic absorption was determined (
(shown as Rh% in Table 4). The conditions and results are shown in Table 4 below. CO:02 mixture of 4 si (96.:4
capacity ratio) to 3. Experiment N. Added at spot time. With the exception of No. 40, the pressure was lowered with the reaction.

Experiment N. 34-36 are not within the scope of this invention and are included for comparison purposes only. Experimental ship. 37-41 illustrate the scope of the invention. Experimental ship. Although no measurable acid was obtained in No. 37, the presence of TOPO was a disgrace to the experiment. Significantly improves the stability of rhodium compared to No. 36. Experiment N.
The conditions of Example 37 include a relatively low O2 partial pressure which is partly responsible for the absence of acid product (see Example 5 to illustrate that acid can be obtained by suitably adjusting conditions other than the O2 partial pressure). Experiment site. Compare 42 and 44). Table 4 Product distribution (9) Note: TOPO has the same meaning as above EtC02H
=Bropionic acid EtCday○--Propionaldehyde (Et
CO)20=propionic anhydride (Et)2CO=diethyl ketone Example 5 Using 0.12 hours of rhodium dicarbonylacetylacetonate, a reaction temperature of 100±3° C. and the conditions shown in Table 5 below, The procedure of Example 4 was repeated.

The amount of product was determined by VPC (within 3% error limits for aldehyde analysis and 10-15% error limit for acid or anhydride analyses) and the results are summarized below. It is shown in Table 5. All of Runs 42-45 illustrate how the present invention and reaction conditions affect product distribution. Note to Table 5: TOP○, Ph, EtcH○,
EtC02 and (EtcO)20 have the same meaning as above. In experiment 44, 40 psi of CO:02 (96:4 volume) was added to the reaction at 3.8 liters. o It is to be understood that the above description is merely illustrative of the invention and that various changes and modifications of the invention will be apparent to those skilled in the art.

Claims (1)

[Claims] 1 Formula ▲ Numerical formulas, chemical formulas, tables, etc. and M represents a group selected from the group consisting of aryl-substituted alkyl groups, and M is phosphorus;
represents a Group V element selected from the group consisting of arsenic and antimony. A method for directly producing at least one of a carboxylic acid and its anhydride from an olefin, the method comprising reacting with carbon oxide, hydrogen and oxygen. 2. The method of claim 1, wherein the olefin is a monoolefin having from 2 to about 12 carbon atoms. 3. The method according to claim 2, wherein the monoolefin is an α-olefin. 4. The method according to claim 2, wherein the monoolefin is an internal olefin. 5 each of R_1, R_2 and R_3 contains at most 15 carbon atoms, and R_1, R_2 and R_3
2. A method according to claim 1, wherein the total number of carbon atoms in is at most 30. 6. The method of claim 5, wherein each of R_1, R_2, and R_3 is a saturated straight chain hydrocarbon group having 5 to 8 carbon atoms. 7. The method of claim 6, wherein M represents phosphorus. 8. The method according to claim 1, wherein the ligand is trioctylphosphine oxide. 9. The method of claim 1, wherein the temperature and total pressure of the reaction are from about 95 to about 110C and from about 250 to about 350 psia, respectively. 10. The method of claim 1, wherein the reaction is carried out in an inert organic solvent. 11. The method according to claim 10, wherein the inert organic solvent is an aliphatic or aromatic hydrocarbon. 12 The inert organic solvent is a saturated aliphatic hydrocarbon having about 9 to about 20 carbon atoms, benzene, and 1 to about 15
11. The method of claim 10, wherein the aromatic hydrocarbon is selected from the group consisting of aromatic hydrocarbons substituted by at least one saturated aliphatic hydrocarbon group having 5 carbon atoms. 13. The method of claim 10, wherein the reaction is carried out by exposing a liquid reaction mixture comprising a solvent and a rhodium complex catalyst to a gas stream comprising oxygen, carbon monoxide, olefin and hydrogen. 14 The molar ratio of oxygen to carbon monoxide to olefin to hydrogen in the gas stream is about 1-5:30-70:5-35:5-3
14. The method according to claim 13, wherein the method is: 15. The method of claim 13, wherein the concentration of catalytically active rhodium in the solvent is from about 25 to about 1,200 ppm, calculated as free metal. 16 The concentration of the ligand in the liquid reaction medium is from about 0.0008 to about 0.08 based on the total volume of the liquid reaction medium.
14. The method of claim 13, wherein the amount is molar. 17 The solvent is about 0.1% based on the weight of the total liquid reaction medium.
14. The method of claim 13, which also contains 5 to about 5% by weight of carboxylic acid. 18. The method according to claim 3, wherein the α-olefin is ethylene. 19. The method according to claim 10, wherein the inert organic solvent is toluene. 20. The method of claim 14, wherein the molar ratio of oxygen to carbon monoxide to ethylene to hydrogen is about 2-3:50-60:20-30:20-30.