CA1043352A - Process for preparing 5-oxo-carboxylic acids - Google Patents
Process for preparing 5-oxo-carboxylic acidsInfo
- Publication number
- CA1043352A CA1043352A CA209,699A CA209699A CA1043352A CA 1043352 A CA1043352 A CA 1043352A CA 209699 A CA209699 A CA 209699A CA 1043352 A CA1043352 A CA 1043352A
- Authority
- CA
- Canada
- Prior art keywords
- ketone
- acrylic acid
- reaction
- methyl
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/185—Saturated compounds having only one carboxyl group and containing keto groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/373—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in doubly bound form
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Abstract of the Disclosure:
Process for preparing 5-oxo-carboxylic acids by reacting ketones with acrylic acids in the presence of ammonia, primary amines, amino-alcohole, amino-carboxylic acids or Schiff's bases as catalysts.
Process for preparing 5-oxo-carboxylic acids by reacting ketones with acrylic acids in the presence of ammonia, primary amines, amino-alcohole, amino-carboxylic acids or Schiff's bases as catalysts.
Description
HOE 73/F_299 lU4;~;~5z The addition of reactive methylene groups to especially activated C,C-double bonds in the presence of basic catalysts is already known. 5-Oxo-carboxylic acid nitriles may be prepared according to this reaction, known as Michael's S addition, by adding ketones having one or several activated hydrogen atoms in O<-position to the especially activated double bond of the acrylonitrile.
5-Oxo-carboxylic acid nitriles may be transformed into 5-oxo-carboxylic acids by hydrolysing them with strong acids, the acids obtained being valuable intermediate products for preparing resorcins and plastics.
This process for preparing 5-oxo-carboxylic acids has the disadvantage that it must be effected in two steps and that ammonium salts are necessarily obtained in the hydrolysis of the nitriles, considerably charging the waste waters.
It could not be expected that ketones could be directly added to the considerably less active double bond of the acrylic acid.
A process has now been found for preparing 5-oxo-carb-oxylic acids of the formula Rl - C - C - CH - CH - COOH
wherein Rl-R5 are identical or di ~erent and each may represent alkyl, cycloalkyl, aryl or aralkyl radicals or, with the exception of Rl, hyrdogen and wherein Rl and R2 or R4 and R5 ~ay form a 5- to 12-membered carbocyclic ring together with the C-C group substituted by them, by reacting ketones of the formula
5-Oxo-carboxylic acid nitriles may be transformed into 5-oxo-carboxylic acids by hydrolysing them with strong acids, the acids obtained being valuable intermediate products for preparing resorcins and plastics.
This process for preparing 5-oxo-carboxylic acids has the disadvantage that it must be effected in two steps and that ammonium salts are necessarily obtained in the hydrolysis of the nitriles, considerably charging the waste waters.
It could not be expected that ketones could be directly added to the considerably less active double bond of the acrylic acid.
A process has now been found for preparing 5-oxo-carb-oxylic acids of the formula Rl - C - C - CH - CH - COOH
wherein Rl-R5 are identical or di ~erent and each may represent alkyl, cycloalkyl, aryl or aralkyl radicals or, with the exception of Rl, hyrdogen and wherein Rl and R2 or R4 and R5 ~ay form a 5- to 12-membered carbocyclic ring together with the C-C group substituted by them, by reacting ketones of the formula
- 2 -~43;~52 ~
l2 Rl - C - CH
o R3 wherein Rl, R2 and R3 have the above meaning, with an acrylic acid of the formula HC = C - COOH
wherein R4 and R5 are defined as above, which comprises carrying out the reaction in the presence of at least one member of the group of ammonia, primary amines, primary aliphatic amino-alcohols, aliphatic amino-carboxylic acids having a primary amino group and Schiff's bases as catalysts.
Examples for the radicals Rl - R5 to be used in the process according to the invention are straight-chained, ramified or cyclic alkyl groups having up to 12, preferably up to 6 carbon atoms, which may be substituted by the phenyl or naphthyl radical. Furthermore Rl - R5 may be aromatic radicals, having up to 14 carbon atoms, preferably the phenyl or naphthyl radical, which may also be substituted, for example, by alkyl, hydroxyl, halogen, alkoxy, cyano and nitro groups. The process can be carried out with or without solvents. Suitable solvents are, for example, acetonitrile, tetrahydrofuran, benzene.
- 5-Oxo-carboxylic acids may be obtained, consequently, in a one-stage reaction, according to this process, without yeilding ammonium salts.
The following amines, amino-alcohols, amino-carboxylic acids and Schiff's bases are examples of the catalysts suitable for the reaction:
_OE 73/F 299 1~)43352 methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, secondary butylamine, tertiary butylamine, amylamine, isoamylamine, ethylidenediamine, tetramethylenediamine, hexamethylenediamine, cyclopentylamine, cyclohexylamine, benzylaminer aminoethanol, glycocoll, B-amino-propionic acid, -amino-caproic acid or the Schiff's bases of the aforesaid amines, preferably those formed by the ketones used.
Generally the quality of the catalysts to be used ranges from 0.01 to 0.2 mol per mol of acrylic acid.
The following ketones, for example, may be used according to the process of the invention: aliphatic ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl isopropyl ketone, methyl-t-butyl-ketone, 2-hexanone, 2-heptanone, 2-octanone, 2-nonanone, acetyl-acetone, acetonyl acetone, cycloaliphatic ketones such as cyclopenta-none, cyclohexanone, l-methyl-2-cyclohexanone, acetophenone, propiophenone and benzyl methyl ketone.
The following acrylic acids, for example, are suitable for the reaction: acrylic acid, methacrylic acid, crotonic acid, ~-methylcrotonic acid, cinnamic acid.
The molar proportion of ketone to acrylic acid may vary within wide limits: it generally ranges from 2 : 1 to 20 : 1, preferably 3 : 1 to 8 : 1.
The reaction can be effected within wide temperature limits. Temperatures from 150 to 230C are the most suitable to assure a good yield and a sufficiently quick reaction.
The pressure is not a critical factor, but the reaction generally is effected at pressures ranging from atmospheric 1~4~35Z 1~ 73/F 299 pressure to 50 atmospheres gauge. If the reaction is carried out in the liquid phase, the process is preferably preferred at the vapor pressure corresponding to the reaction tempera-ture. It is also possible to operate in the gaseous phase.
The acrylic acid used may be reacted completely or partially. Preferably the reaction rate should not surpass 90%, since otherwise the extended reaction time and the higher reaction temperatures necessary for a reaction rate above 90% are susceptible to favour secondary reactions.
The fraction obtained in the separation of the reaction products by distillation containing the non-reacted starting material and the catalyst can be re-used for the reaction.
The following examples illustrate the invention.
E X A M P L E 1:
2.320 g (40 mols) of acetone, 576 g (8 mols) of acrylic acid, 42 g (0.7 mol) of isoproylamine and 2 g of hydroquinone are heated to 180C for two hours in a 5 liter autoclave provided with a stirrer and cooled subsequently. The gas-chromatographic analysis of the reaction product (2.920 g) showed the following composition: 70.8~ by weight of acetone, 14.6% by weight of 5-oxo-hexanoic acid, 8.2~ by weight of acrylic acid. The conversion of the acrylic acid was 58.4~ and of the acetone 10.9%.
The yield of 5-oxo-hexanoic acid, calculated on the converted acrylic acid, was 70.2% and, calculated on the converted acetone, 75.3~.
E X A M P L E 2:
720 g (10 mols) of methyl ethyl ketone, 144 g (2 mols) of acrylic acid, 21 g (0.35 mol) of isopropyplamine and I~OE 73/F 299 lV4;~35Z ~
2 g of hydroquinone were heated to 185C for 1 hour in a 2 liter autoclave. The reaction product (890 g) had the fol-lowing composition: 67.8% by weight of methyl ethyl ketone, 16.2% by weight of methyl-5-oxo-hexanoic acid, 4.0% by weight of 5-oxo-heptanoic acid and 3.0% by weight of acrylic acid.
The reaction rate of the acrylic acid was 81.5% and of the methyl ethyl ketone 16.2%. The yield of 4-methyl-5-oxo-hexanoic acid, calculated on the reacted acrylic acid, was 62% and, calculated on the reacted methyl ethyl ketone, 60%. The yield of 5-oxo-heptanoic acid was 15.5%, calcu-lated on the reacted acrylic acid and 15%, calculated on the reacted methyl ethyl ketone.
l2 Rl - C - CH
o R3 wherein Rl, R2 and R3 have the above meaning, with an acrylic acid of the formula HC = C - COOH
wherein R4 and R5 are defined as above, which comprises carrying out the reaction in the presence of at least one member of the group of ammonia, primary amines, primary aliphatic amino-alcohols, aliphatic amino-carboxylic acids having a primary amino group and Schiff's bases as catalysts.
Examples for the radicals Rl - R5 to be used in the process according to the invention are straight-chained, ramified or cyclic alkyl groups having up to 12, preferably up to 6 carbon atoms, which may be substituted by the phenyl or naphthyl radical. Furthermore Rl - R5 may be aromatic radicals, having up to 14 carbon atoms, preferably the phenyl or naphthyl radical, which may also be substituted, for example, by alkyl, hydroxyl, halogen, alkoxy, cyano and nitro groups. The process can be carried out with or without solvents. Suitable solvents are, for example, acetonitrile, tetrahydrofuran, benzene.
- 5-Oxo-carboxylic acids may be obtained, consequently, in a one-stage reaction, according to this process, without yeilding ammonium salts.
The following amines, amino-alcohols, amino-carboxylic acids and Schiff's bases are examples of the catalysts suitable for the reaction:
_OE 73/F 299 1~)43352 methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, secondary butylamine, tertiary butylamine, amylamine, isoamylamine, ethylidenediamine, tetramethylenediamine, hexamethylenediamine, cyclopentylamine, cyclohexylamine, benzylaminer aminoethanol, glycocoll, B-amino-propionic acid, -amino-caproic acid or the Schiff's bases of the aforesaid amines, preferably those formed by the ketones used.
Generally the quality of the catalysts to be used ranges from 0.01 to 0.2 mol per mol of acrylic acid.
The following ketones, for example, may be used according to the process of the invention: aliphatic ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl isopropyl ketone, methyl-t-butyl-ketone, 2-hexanone, 2-heptanone, 2-octanone, 2-nonanone, acetyl-acetone, acetonyl acetone, cycloaliphatic ketones such as cyclopenta-none, cyclohexanone, l-methyl-2-cyclohexanone, acetophenone, propiophenone and benzyl methyl ketone.
The following acrylic acids, for example, are suitable for the reaction: acrylic acid, methacrylic acid, crotonic acid, ~-methylcrotonic acid, cinnamic acid.
The molar proportion of ketone to acrylic acid may vary within wide limits: it generally ranges from 2 : 1 to 20 : 1, preferably 3 : 1 to 8 : 1.
The reaction can be effected within wide temperature limits. Temperatures from 150 to 230C are the most suitable to assure a good yield and a sufficiently quick reaction.
The pressure is not a critical factor, but the reaction generally is effected at pressures ranging from atmospheric 1~4~35Z 1~ 73/F 299 pressure to 50 atmospheres gauge. If the reaction is carried out in the liquid phase, the process is preferably preferred at the vapor pressure corresponding to the reaction tempera-ture. It is also possible to operate in the gaseous phase.
The acrylic acid used may be reacted completely or partially. Preferably the reaction rate should not surpass 90%, since otherwise the extended reaction time and the higher reaction temperatures necessary for a reaction rate above 90% are susceptible to favour secondary reactions.
The fraction obtained in the separation of the reaction products by distillation containing the non-reacted starting material and the catalyst can be re-used for the reaction.
The following examples illustrate the invention.
E X A M P L E 1:
2.320 g (40 mols) of acetone, 576 g (8 mols) of acrylic acid, 42 g (0.7 mol) of isoproylamine and 2 g of hydroquinone are heated to 180C for two hours in a 5 liter autoclave provided with a stirrer and cooled subsequently. The gas-chromatographic analysis of the reaction product (2.920 g) showed the following composition: 70.8~ by weight of acetone, 14.6% by weight of 5-oxo-hexanoic acid, 8.2~ by weight of acrylic acid. The conversion of the acrylic acid was 58.4~ and of the acetone 10.9%.
The yield of 5-oxo-hexanoic acid, calculated on the converted acrylic acid, was 70.2% and, calculated on the converted acetone, 75.3~.
E X A M P L E 2:
720 g (10 mols) of methyl ethyl ketone, 144 g (2 mols) of acrylic acid, 21 g (0.35 mol) of isopropyplamine and I~OE 73/F 299 lV4;~35Z ~
2 g of hydroquinone were heated to 185C for 1 hour in a 2 liter autoclave. The reaction product (890 g) had the fol-lowing composition: 67.8% by weight of methyl ethyl ketone, 16.2% by weight of methyl-5-oxo-hexanoic acid, 4.0% by weight of 5-oxo-heptanoic acid and 3.0% by weight of acrylic acid.
The reaction rate of the acrylic acid was 81.5% and of the methyl ethyl ketone 16.2%. The yield of 4-methyl-5-oxo-hexanoic acid, calculated on the reacted acrylic acid, was 62% and, calculated on the reacted methyl ethyl ketone, 60%. The yield of 5-oxo-heptanoic acid was 15.5%, calcu-lated on the reacted acrylic acid and 15%, calculated on the reacted methyl ethyl ketone.
Claims (8)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1, A process for the preparation of a 5-oxo-carboxylic acid in which a ketone selected from the group of acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl isopropyl ketone, methyl-t-butyl-ketone, 2-hexanone, 2-heptanone, 2-octanone, 2-nonanone, acetyl-acetone, acetonyl acetone, cyclopentanone, cyclohexanone, 1-methyl-2-cyclohexanone, acetophenone, propiophenone and benzyl methyl ketone is reacted with an acrylic acid selected from the group of acrylic acid, meth-acrylic acid, crotonic acid, .alpha.-methylcrotonic acid and cinnamic acid in the presence of at least one catalyst of the group of ammonia, primary amines, primary aliphatic amino-alcohols, primary amino-carboxylic acids having a primary amino group and Schiff's bases.
2. A process as claimed in claim 1, in which the reaction is carried out at a temperature from 150° to 230°C.
3. A process as claimed in claim 1, in which the reaction is carried out at a pressure from 1 to 50 atmospheres gauge.
4. A process as claimed in claim 1, claim 2 or claim 3, in which the catalyst is present in an amount of from 0.01 to 0.2 mol per mol of the acrylic acid.
5. A process as claimed in claim 1, claim 2 or claim 3, in which the molar proportion of the ketone to the acrylic acid is in the range of from 2:1 to 20:1.
6. A process as claimed in claim 1, claim 2 or claim 3, in which the molar proportion of the ketone to the acrylic acid is in the range of from 3:1 to 8:1.
7. A process as claimed in claim 1, claim 2 or claim 3, in which the reaction is carried out in the gaseous phase.
8. A process as claimed in claim 1, claim 2 or claim 3, in which the reaction is carried out in the liquid phase.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2348536A DE2348536C3 (en) | 1973-09-27 | 1973-09-27 | Process for the preparation of 5-oxocarboxylic acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1043352A true CA1043352A (en) | 1978-11-28 |
Family
ID=5893770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA209,699A Expired CA1043352A (en) | 1973-09-27 | 1974-09-20 | Process for preparing 5-oxo-carboxylic acids |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS5844650B2 (en) |
| BE (1) | BE820449A (en) |
| BR (1) | BR7407939D0 (en) |
| CA (1) | CA1043352A (en) |
| CH (1) | CH605558A5 (en) |
| DE (1) | DE2348536C3 (en) |
| FR (1) | FR2245605B1 (en) |
| GB (1) | GB1476153A (en) |
| IT (1) | IT1022317B (en) |
| NL (1) | NL7412470A (en) |
| ZA (1) | ZA745966B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7808605A (en) * | 1978-08-19 | 1980-02-21 | Stamicarbon | PROCESS FOR THE PREPARATION OF DELTA KETO ACIDS AND THEIR DERIVATIVES. |
| DE2921430A1 (en) * | 1979-05-26 | 1980-12-04 | Haarmann & Reimer Gmbh | 3-METHYL-5-KETO- ALPHA, OMEGA -ALKEN- DICARBONIC ACIDS, METHOD FOR THEIR PRODUCTION AND THEIR USE FOR THE PRODUCTION OF MACROCYCLIC BETA-METHYL-KETONE |
| JPS60152440A (en) * | 1984-01-21 | 1985-08-10 | Sumitomo Chem Co Ltd | Production of delta-oxocarboxylic acid and its derivative |
-
1973
- 1973-09-27 DE DE2348536A patent/DE2348536C3/en not_active Expired
-
1974
- 1974-09-20 NL NL7412470A patent/NL7412470A/en not_active Application Discontinuation
- 1974-09-20 ZA ZA00745966A patent/ZA745966B/en unknown
- 1974-09-20 CA CA209,699A patent/CA1043352A/en not_active Expired
- 1974-09-24 CH CH1289374A patent/CH605558A5/xx not_active IP Right Cessation
- 1974-09-25 IT IT27712/74A patent/IT1022317B/en active
- 1974-09-25 BR BR7939/74A patent/BR7407939D0/en unknown
- 1974-09-26 JP JP49110068A patent/JPS5844650B2/en not_active Expired
- 1974-09-27 BE BE148988A patent/BE820449A/en unknown
- 1974-09-27 FR FR7432636A patent/FR2245605B1/fr not_active Expired
- 1974-09-27 GB GB4204474A patent/GB1476153A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2348536B2 (en) | 1978-07-20 |
| NL7412470A (en) | 1975-04-02 |
| CH605558A5 (en) | 1978-09-29 |
| IT1022317B (en) | 1978-03-20 |
| JPS5844650B2 (en) | 1983-10-04 |
| DE2348536A1 (en) | 1975-04-03 |
| BE820449A (en) | 1975-03-27 |
| DE2348536C3 (en) | 1979-03-29 |
| JPS5059323A (en) | 1975-05-22 |
| ZA745966B (en) | 1975-11-26 |
| FR2245605A1 (en) | 1975-04-25 |
| FR2245605B1 (en) | 1979-02-02 |
| GB1476153A (en) | 1977-06-10 |
| BR7407939D0 (en) | 1975-07-29 |
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