GB2101128A - Process for the production of alcohols and carboxylic group-containing compounds - Google Patents
Process for the production of alcohols and carboxylic group-containing compounds Download PDFInfo
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- GB2101128A GB2101128A GB08216734A GB8216734A GB2101128A GB 2101128 A GB2101128 A GB 2101128A GB 08216734 A GB08216734 A GB 08216734A GB 8216734 A GB8216734 A GB 8216734A GB 2101128 A GB2101128 A GB 2101128A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/02—Monohydroxylic acyclic alcohols
- C07C31/04—Methanol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/02—Monohydroxylic acyclic alcohols
- C07C31/08—Ethanol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/02—Monohydroxylic acyclic alcohols
- C07C31/10—Monohydroxylic acyclic alcohols containing three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
A process for the production of an alcohol having m carbon atoms and a carboxylate group-containing compound having n carbon atoms from an aldehyde having n carbon atoms and either an aldehyde or a ketone having m carbon atoms, m and n being integers and m being greater than n, comprises reacting in an aqueous medium the aldehyde having n carbon atoms with either the aldehyde or the ketone having m carbon atoms in the presence of a catalyst comprising a complex of a noble transition metal.
Description
SPECIFICATION
Process for the production of alcohols and carboxylic group-containing compounds
The present invention relates to a process for the production of a mixture of alcohols and carboxylate group-containing compounds.
Both alcohols, eg ethanol, propanol and butanol, and carboxylate group-containing compounds, eg carboxylic acids such as formic acid, acetic acid and propionic acid are valuable industrial products. Ethanol for example is generally manufactured on a large scale either by fermentation of natural products, eg molasses, or by hydration of ethylene in the presence of an acid catalyst such as phosphoric acid supported on silica. Carboxylic acids such as acetic acid are generally manufactured either by oxidation of paraffinic feedstocks at elevated temperature and pressure or by reacting an alcohol with carbon monoxide in the presence of a rhodium catalyst promoted with a halogen compound. Alternative routes to ethanol and acetic acid, especially ones which utilise milder reaction conditions, are constantly under investigation.
In this context our GB patent application No 2054592A describes a process for the production of both an alcohol and a compound containing a carboxylate group which process comprises contacting an aldehyde in neutral or alkaline aqueous medium with a catalyst comprising a complex of a noble metal. Using acetaldehyde as the aldehyde reactant the products are ethanol and either acetic acid in neutral aqueous medium or an acetate salt in alkaline aqueous medium. The general reaction maybe represented by the equation:
2RCHO + OH- = RCH2OH + RCOO- (I)
That these products are formed is somewhat surprising because in aqueous alkali only aldehydes not having hydrogen on the carbon atom alpha- to the aldehyde group are susceptible to the reaction and in a neutral aqueous medium the reaction does not generally take place at all.Moreover aldehydes having alpha-CH bonds generally undergo the base-catalysed aldol condensation in aqueous alkaline media by preference.
For example the aldol condensation of acetaldehyde may be presented by the equation:
OH -H2O 2CHsCHO = CH3CH(OH)CH2CHO = CH3CH:CHCHO (II) It has now been found that aldehydes containing n carbon atoms react with either aldehydes or ketones containing m carbon atoms in acids, where m and n are integers and m is greater than n, neutral and alkaline aqueous media in the presence of a complex of a noble metal as catalyst to produce the alcohol corresponding to the aldehyde or ketone containing m carbon atoms and a carboxylate group-containing compound, ie a carboxylic acid in neutral or acid media or a carboxylate salt in alkaline media, corresponding to the aldehyde containing n carbon atoms.
Accordingly, the present invention provides a process for the production of an alcohol having m carbon atoms and a carboxylate group-containing compound having n carbon atoms from an aldehyde having n carbon atoms and either an aldehyde or a ketone having m carbon atoms, m and n being integers and m being greater than n, which process comprises reacting in an aqueous medium the aldehyde having n carbon atoms with either the aldehyde or the ketone having m carbon atoms in the presence of a catalyst comprising a complex of a noble transition metal.
In addition to the alcohol having m carbon atoms, disproportionation of the individual aldehydes or ketones may lead to other products, including alcohols and carboxylate group-containing compounds, by the reaction illustrated in equation (I).
The aldehyde reactants may suitably be aliphatic or aromatic aldehydes and, moreover, may or may not contain hydrogen on the carbon atom alpha- to the aldehyde function. Suitable aldehydes which may be used in the process of the invention include formaldehyde, acetaldehyde, propionaldehyde and benzaldehyde, provided that two aldehydes of differing carbon number are employed. For example formaldehyde may be reacted with acetaldehyde, propionaldehyde etc. The reaction in aqueous alkaline media (excluding simple homodisproportionation of aldehydes) may be represented by the equation:
HCO + MeCHO + OH = HCO2 + MeCH2OH (Ill) Any ketone or higher carbon number than the reactant aldehyde may be employed. Thus when the aldehyde is formaldehyde or acetaldehyde the ketone may suitably be acetone.The reaction in aqueous alkaline media (excluding simple homodisproportionation of aldehyde) may be represented by the equation:
RCHO + Me2CO + OH- = RCO2- Me2CHOH (IV) wherein R = H or Me.
The aldehyde having n carbon atoms may be reacted with the aldehyde or ketone having m carbon atoms in quite wide proportions, though it is preferred to employ a molar excess of the m carbon atom material. For example, using formaldehyde and acetone as the reactants it is preferred to employ a molar ratio of 1:4.
The aqueous medium employed may be acidic, neutral or alkaline. Preferably the pH of the aqueous medium is greater than 7, more preferably in the range 8 to 12 and even more preferably in the range fom 10 to 12.
Within the context of the present specification the noble transition metals are defined as palladium, platinum, rhodium, ruthenium, osmium and iridium. The preferred noble transition metals are rhodium, ruthenium and iridium. The noble transition metal complex is preferably soluble in the aqueous medium under the conditions of the reaction.Suitable noble transition metal complexes include [Rh2(C5Me5)2(OH)31 Cl.4H20, [Fh2(C5Me5)2C14], [Ru2(C6Me6)2(OH)3]Cl.4H2O, [Rh2(C5Me5)2(H)(OCOR)2]+Z wherein R = alkyl or aryl and Z- is a non-coordinating anion, [Ru2(C6Me6)2(OCOR)3]Z wherein R = alkyl or aryl and Z- is a non-coordinating anion, as well as other catalysts of the general type [Rh2(arene)2X4] wherein Xis halogen and arene is benzene, p-cymene, etc. The complexes may be prepared by methods well known in the art.
Thus the complex RH2(C5Me5)2(OH)3 C1.4H2O which is a stable, crystalline, orange solid may be prepared by reacting [Rh2(C5Me5)2C14) with aqueous sodium hydroxide. The preparation of both this and the complex [Rh2(C5Me5)C14] is described in detail in Accts. Chem. Res., 1978, 11,301 (P.M. Maitlis); J. Amer. Chem. Soc., 1969,91,5970 (J.W. Kang, K. Moseley and P.M. Maitlis) and J. Organometallic Chem. 1971,26,393. The complex [Ru2(C6Me6)2(OH1)3]Cl.4H2O may be prepared by reacting the complex [Ru2(C6Me6)2Cl4] which has been described in JCS Chem. Comm., 1978, 582 (M.A. Bennett, T-N Huang, A. K. Smith and T.W. Turney) with aqueous sodium carbonate. The transition metal complex may be supported on an inert support if so desired.
Ligands may be added for the purpose of adjusting the relative proportions of the various products.
Suitable ligands include tertiary phosphines, in particular phosphines having the formula R3P, and tertiary amines of formula R3N, wherein R is independently a hydrocarbyl group. Suitably the phosphine may be triphenylphosphine. Suitably the molar ratio of the ligand to the noble metal complex may be in the range 0.1:1 to 100:1, preferably from 1:1 to 3:1.
The use of an inert co-solvent may be advantageous, particularly when one or more of the reactants is sparingly soluble, or insoluble in water. Such a reactant is 2-butanone. A suitable co-solvent is 2-propanol.
The molar ratio of total aldehyde or total aldehyde and ketone to catalyst in the reaction mixture may suitably be in the range 1:1 to 5000:1, preferably from 50:1 to 500:1. The amount of the aqueous medium employed is not critical to the performance of the invention provided that sufficient is present to carry out the process. On the other hand an excessive amount of aqueous medium is not desirable because it unnecessarily burdens product separation and recovery.
The process may suitably be carried out at atmospheric pressure, through sub-atmospheric and super-atmospheric pressures may be employed if so desired. The reaction temperature may suitably be in the range 0 to 300 C, preferably in the range 5 to 200 C.
The process may be carried out batchwise or continuously. The products may be recovered from the reaction mixture and separated in known manner.
The invention will now be illustrated by reference to the following Examples.
Example 1
0.04 m moles of [Rh2(C5Me5)2(OH)3CI.4H2O dissolved in aqueous sodium hydroxide (0.5 M, 5 cm3) was added to a solution of acetaldehyde (2.3 m moles) and formaldehyde (2.3 m moles) in water (1 cm3). After 10 minutes at 20"C the solution was analysed by 1 H NMR spectroscopy and gas chromatography. This showed the presence of ethanol (2.0 m moles), methanol (0.3 m moles), sodium formate (2.0 m moles) and sodium acetate (0.4 m moles).
Example 2
Example 1 was repeated except that [Ru2(p-cymene)2C14] (0.04 m moles) was used in place of [Rh2(CSMe5)2(0H)3CI4H20.
Example 3
Example 1 was repeated except that [lr2(C5Me5)2Cl4] (0.04 m moles) was used in place of [Rh2(C5Me5)2(OH)3]Cl.4H2O.
Example 4
0.04 m moles of [Rh2(C5Me5)2(OH)3]Cl.4H2O dissolved in aqueous sodium hydroxide (0.5 M, 5 cm3) was added to a solution of formaldehyde (0.46 m moles) and propionaldehyde (0.46 m moles) in water (1 cm3).
The solution was analysed after 3 minutes at 20"C by 1H NMR spectroscopy and gas chromatography.
Example 5
Example 4 was repeated except that the formaldehyde was replaced by acetaldehyde (0.46 m moles).
Example 6
0.04 m moles of [Rh2(C5Me5)2(OH)31Cl.4H2O dissolved in aqueous sodium hydroxide (0.5 M, cm3) was added to a solution of acetone (2.3 m moies) and formaldehyde (2.3 m moles) in water (1 cm3). After 10 minutes at 200C the solution was analysed by 1NMR spectroscopy and gas chromatography.
Example 7
Example 6 was repeated using [Ru2(p-cymene)2Cl4] (0.04 m moles) in place of [Rh2(C5Me5)2(OH)3]Cl.4H2O.
Example 8
Example 6 was repeated using [lr2(C5Me5)2Cl4] (0.04 m moles) in place of [Rh2(C5Me5)2(OH)3jCI.4H2O.
Example 9
Example 6 was repeated using acetaldehyde in place of the formaldehyde.
The results of Examples 1 to 9 are given in Table 1.
Example 10
0.04 m moles [Rh2(C5Me5)2(OH)3]Cl.4H2O, formaldehyde (10.7 m moles) and acetaldehyde (10.7 m moles) in water (6 cm3) were reacted at 50"C for 24 hours. The solution was then analysed by 1H NMR spectroscopy and gas chromatography.
Example 11 Example 10 was repeated except that formaldehyde (2.5 m moles) and propionaldehyde (2.5 m moles) were used in place of formaldehyde (10.7 m moles) and acetaldehyde (10.7 m moles).
Example 12
Example 10 was repeated except that acetaldehyde was replaced by acetone (10.7 m moles).
Example 13
Example 10 was repeated except that formaldehyde was replaced by acetone (10.7 m moles).
The results of Examples 10 to 13 are given in Table 2.
TABLE 1
Example Catalyst Reactants Products
No (m mol) (m mol) 1 [RhC5Me5)2(OH)3]Cl.4H2O MeCHO (2.3 EtOH (2.0) MeCO2Na (0.4)
HCHO (2.3) MeOH (0.3) HCO2Na (2.0)
2 [Ru p-cymene)2Cl4] MeCHO (2.3) EtOH (0.3) MeCO2Na (0.2)
HCHO (2.3) MeOH (0.1) HCO2Na (0.3)
3 [(lrC5Me5)2Cl4] MeCHO (2.3) EtOH (0.7) MeCo2Na (0.4)
HCHO (2.3) MeOH (0.4) HCO2Na (0.7)
4 [(RhC5Me5)2(OH)3]Cl.4H2O EtCHO (0.46) n-PrOH (0.42) EtCO2Na (trace)
HCHO (0.46) MeOH (0.06) HCO2Na (0.42)
5 [(RhC5Me5)2(OH)3jC1.4H2O EtCHO (0.46) n-PrOH (0.27) MeCO2Na (0.28)
MeCHO (0.46) EtOH (0.22)
6 [(RhCMe5)2(OH)3]Cl.4H2O Me2CO (2.3) i-PrOH (0.5) HCO2Na (1.6)
HCHO (2.3) MeOH (0.6)
7 [(Ru p-cymene)2Cl4] Me2CO (2.3) i-PrOH (0.2) HCO2Na (0.8)
HCHO (2.3) MeOH (0.5)
8 [(IrC5Me5)2CI4] Me2CO (2.3) i-PrOH (0.1) HCO2Na (1.2)
HCHO (2.3) MeOH (0.6)
9 [(RhC5Me5)2(OH)3]CI.4H2O Me2CO (2.3) i-PrOH (0.2) MeCO2Na (1.2)
MeCHO (2.3) EtOH (1.0)
TABLE 2
Example Catalyst Reactants Products
No (m mol) (m mol)
10 [(RhC5Me5)2(OH)3C1.4H2O MeCHO (10.7) EtOH (5.6) MeCO2H (1.2)
HCHO (10.7) MeOH (trace) HCO2H (trace)
11 [(RhC5Me5)2(OH)3]CI.4H2O EtCHO (2.5) n-PrOH (1.3) EtCOH (0.3)
HCHO (2.5) MeOH (trace) HCO2H (trace)
12 [(RhC5Me5)2(OH)3]Cl.4H2O Me2CO (10.7) i-PrOH (1.9)
HCHO (10.7) MeOH (trace) HCO2H (trace)
13 [(RhC5Me5)2(OH)3]Cl.4H2O Me2CO (10.7) i-PrOH (0.5)
MeCHO (10.7) EtOH (2.5) MeCO2H (3.3)
Claims (15)
1. A process for the production of an alcohol having m carbon atoms and a carboxylate group-containing compound havng n carbon atoms from an aldehyde having n carbon atoms and either an aldehyde or a ketone having m carbon atoms, m and n being integers and m being greater than n, which process comprises reacting in an aqueous medium the aldehyde having n carbon atoms with eitherthe aldehyde or the ketone having m carbon atoms in the presence of a catalyst comprising a complex of a noble transition metal.
2. A process according to claim 1 wherein the aldehyde having n carbon atoms is formaldehyde.
3. A process according to either one of the preceding claims wherein the aldehyde having m carbon atoms is either acetaldehyde, propionaldehyde or benzaldehyde.
4. A process according to claim 1 wherein the aldehyde having n carbon atoms is formaldehyde or acetaldehyde and the ketone having m carbon atoms is acetone.
5. A process according to any one of the preceding claims wherein the pH of the aqueous medium is greater than 7.
6. A process according to claim 5 wherein the pH is in the range 8 to 12.
7. A process according to any one of the preceding claims wherein the noble transition metal is rhodium, ruthenium or iridium.
8. A process according to any one of the preceding claims wherein the noble transition metal complex is soluble in the aqueous medium.
9. A process according to any one of the claims 1 to 7 wherein the noble transition metal complex is supported on an inert support.
10. A process according to any one of the previous claims wherein a ligand is added.
11. A process according to claim 10 wherein the ligand is a tertiary phosphine of formula R3P or a tertiary amine of formula R3N, wherein in the formulae R is independently a hydrocarbyl group.
12. A process according to either claim 10 or claim 11 wherein the molar ratio of the ligand to the noble metal complex is in the range from 1:1 to 3:1.
13. A process according to any one of the preceding claims wherein the molar ratio of total aldehyde or total aldehyde plus ketoneto catalyst in the reaction mixture is in the range from 50:1 to 500:1.
14. A process according to any one of the preceding claims wherein the reaction temperature is in the range from 5 to 2000C.
15. A process according to any one of the preceding claims wherein an inert co-solvent is employed.
A A process according to claim 15 wherein the co-solvent is 2-propanol.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8117632 | 1981-06-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB2101128A true GB2101128A (en) | 1983-01-12 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08216734A Withdrawn GB2101128A (en) | 1981-06-09 | 1982-06-09 | Process for the production of alcohols and carboxylic group-containing compounds |
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| Country | Link |
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| GB (1) | GB2101128A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017208098A1 (en) * | 2016-05-31 | 2017-12-07 | Sabic Global Technologies B.V. | Production of acetic acid and hydrogen in an aqueous medium from ethanol and acetaldehyde via an organic/inorganic catalyst |
-
1982
- 1982-06-09 GB GB08216734A patent/GB2101128A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017208098A1 (en) * | 2016-05-31 | 2017-12-07 | Sabic Global Technologies B.V. | Production of acetic acid and hydrogen in an aqueous medium from ethanol and acetaldehyde via an organic/inorganic catalyst |
| CN109195937A (en) * | 2016-05-31 | 2019-01-11 | 沙特基础工业全球技术公司 | Acetic acid and hydrogen are generated in water-bearing media by ethyl alcohol and acetaldehyde by organic/inorganic catalyst |
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| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |