GB782430A - Improvements in the oxidation of organic aldehydes - Google Patents
Improvements in the oxidation of organic aldehydesInfo
- Publication number
- GB782430A GB782430A GB33254/54A GB3325454A GB782430A GB 782430 A GB782430 A GB 782430A GB 33254/54 A GB33254/54 A GB 33254/54A GB 3325454 A GB3325454 A GB 3325454A GB 782430 A GB782430 A GB 782430A
- Authority
- GB
- United Kingdom
- Prior art keywords
- acids
- alkali
- aldehyde
- catalyst
- ethyl
- 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
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring 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
-
- 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
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
-
- 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
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
-
- 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
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
-
- 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
- C07C59/01—Saturated compounds having only one carboxyl group and containing hydroxy or O-metal groups
-
- 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
- C07C59/125—Saturated compounds having only one carboxyl group and containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- 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)
Abstract
Aldehydes are oxidized by simultaneously and separately introducing an organic aldehyde and a strong alkali into an aqueous suspension of a silver catalyst, the strong alkali being employed in an amount of at least one chemical equivalent for each equivalent of the aldehyde, and passing molecular oxygen through such mixture while maintaining the reaction mixture at a pH of at least 12.5 and at a temperature of at least 20 DEG C., the catalyst being present in a concentration of at least 1 per cent by weight of the reaction mixture. On completion of the oxidation the product acid is liberated from its salt by addition of a strong acid such as sulphuric, hydrochloric, nitric or phosphoric acids. Formic or acetic acid may also be used to liberate weaker or water-insoluble acids. The process may be used for the production of any carboxylic acid such as saturated and unsaturated aliphatic acids, e.g. sorbic, acrylic, methacrylic, crotonic, 2-ethyl-2-butenoic, 2-hexenoic, 2-methyl-2-pentenoic, 2-octenoic, 2 - ethyl - 2 - hexenoic, 2,4,6 - octatrienoic, butyric, hexanoic, 2-ethylbutyric, 2-ethyl-hexanoic, 2-ethyloctanoic and 2-butylhexanoic acids; hydroxy and alkoxy acids, e.g.22-butoxybutyric, 3,5 - diethoxyhexanoic and 2-ethyl-3 hydroxyhexanoic acids; dibasic acids such as glutaric, 3-methylglutaric and 2-ethylglutaric acids; cyclic unsaturated acids, e.g. D 3-tetrahydrobenzoic, D 3-tetrahydro-o-toluic, 2,3-dihydro - 1,4 - pyran - 2 - carboxylic, 2,3-dimethyl - 2,3 - dihydro - 1,4 - pyran - 2 - carboxylic acid and furoic acids; and aromatic acids, e.g. benzoic, salicyclic, cinnamic and p-chlorobenzoic acids. The preferred alkali for use in the process is sodium hydroxide, although lithium, potassium, or barium hydroxides may also be used. The alkali is generally used in an amount of 1-2, preferably 1-1.2 equivalent per equivalent of aldehyde, sufficient being employed to maintain in the reaction mixture a pH of at least 12.5 at all times. The aldehyde and strong alkali are preferably added continuously to a vigorously agitated aqueous suspension of the silver catalyst. The rate of addition of aldehyde should not exceed the rate of which it is oxidized, rates up to 8 pounds per hour per gallon of reaction mixture being suitable. The oxygen may be used in pure form or mixed with other gases as in air, and is preferably used in large excess. The finely divided silver catalyst may be preformed by reduction of silver oxide or a silver salt such as silver nitrate by reaction with an aldehyde and alkali, hydrogen peroxide and alkali, or with aluminium and alkali. The catalyst may also be prepared in situ by adding silver oxide or nitrate to the reaction mixture, the reduction being effected by the aldehyde and alkali. The preferred catalyst concentration is 3 to 10 per cent by weight of the reaction mixture. The reaction is generally effected at 20-100 DEG C., preferably 20-80 DEG C., and pressures from atmospheric to 150 p.p.i.g. are suitable. Pressures in excess of 200 p.p.s.i.g. may also be used. When using air it is necessary to operate at a higher pressure than when using pure oxygen to obtain the same result. The process may be operated batchwise or continuously. In the preferred continuous operation, the product salt solution is continuously withdrawn via an internal filter to eliminate the necessity for recycling the catalyst. When the catalyst becomes inactive it may be reactivated by washing with organic solvents and inorganic solutions. After liberation of the acid from the salt, the acid may be recovered by any appropriate method, such as filtration, solvent extraction, distillation or decantation. Detailed examples are given for the continuous oxidation under varying conditions of hexadienal, acrolein, methacrolein, crotonaldehyde, 2-ethylcrotonaldehyde, 2-hexanal, 2-methyl-2-pentenal, 2-octenal, 2-ethyl-2-hexenal, a mixture of C8 unsaturated aldehydes containing 2,4,6-octatrienal; 4-pentenal, 2-ethylbutyraldehyde, 2-ethylhexaldehyde, 2-ethyloctaldehyde, a mixture of 2-ethyloctaldehyde and 2-butylhexaldehyde; 3-butoxybutyraldehyde, 3,5 - diethoxyhexaldehyde, butyraldol - (2-ethyl - 3 - hydroxyhexaldehyde), glutaraldehyde, 3 - methylglutaraldehyde, 2 - ethyl - 3-methylglutaraldehyde, 2 - ethylglutaraldehyde, D 3 - tetrahydrobenzaldehyde, D 3 - tetrahydro - o - tolualdehyde, acrolein dimer, methacrolein dimer, furfural, benzaldehyde, salicylaldehyde, cinnamaldehyde, and p-chlorobenzaldehyde.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US782430XA | 1953-11-19 | 1953-11-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB782430A true GB782430A (en) | 1957-09-04 |
Family
ID=22142818
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB33254/54A Expired GB782430A (en) | 1953-11-19 | 1954-11-17 | Improvements in the oxidation of organic aldehydes |
Country Status (2)
Country | Link |
---|---|
GB (1) | GB782430A (en) |
NL (1) | NL93607C (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3162682A (en) * | 1959-12-28 | 1964-12-22 | Cities Service Res & Dev Co | Disproportionation reaction of alpha, beta-ethylenically unsaturated aldehydes in the presence of a silver catalyst |
EP0170520A2 (en) * | 1984-07-30 | 1986-02-05 | Sumitomo Chemical Company, Limited | Process for the production of cinnamic acid |
EP0439013A1 (en) * | 1990-01-04 | 1991-07-31 | Praxair Technology, Inc. | Enhanced gas-liquid reactions |
EP0571864A2 (en) * | 1992-05-29 | 1993-12-01 | Bayer Ag | Process for the preparation of alpha,beta unsaturated carboxylic acids |
FR2769624A1 (en) * | 1997-10-09 | 1999-04-16 | Atochem Elf Sa | A new process for the preparation of a carboxylic acid |
WO2011020878A3 (en) * | 2009-08-21 | 2011-09-15 | Basf Se | Method for producing 4-pentenoic acid |
-
0
- NL NL93607D patent/NL93607C/xx active
-
1954
- 1954-11-17 GB GB33254/54A patent/GB782430A/en not_active Expired
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3162682A (en) * | 1959-12-28 | 1964-12-22 | Cities Service Res & Dev Co | Disproportionation reaction of alpha, beta-ethylenically unsaturated aldehydes in the presence of a silver catalyst |
EP0170520A2 (en) * | 1984-07-30 | 1986-02-05 | Sumitomo Chemical Company, Limited | Process for the production of cinnamic acid |
EP0170520A3 (en) * | 1984-07-30 | 1987-04-15 | Sumitomo Chemical Company, Limited | Process for the production of cinnamic acid |
EP0439013A1 (en) * | 1990-01-04 | 1991-07-31 | Praxair Technology, Inc. | Enhanced gas-liquid reactions |
EP0571864A2 (en) * | 1992-05-29 | 1993-12-01 | Bayer Ag | Process for the preparation of alpha,beta unsaturated carboxylic acids |
EP0571864A3 (en) * | 1992-05-29 | 1995-04-05 | Bayer Ag | Process for the preparation of alpha,beta unsaturated carboxylic acids. |
FR2769624A1 (en) * | 1997-10-09 | 1999-04-16 | Atochem Elf Sa | A new process for the preparation of a carboxylic acid |
WO2011020878A3 (en) * | 2009-08-21 | 2011-09-15 | Basf Se | Method for producing 4-pentenoic acid |
CN102574763A (en) * | 2009-08-21 | 2012-07-11 | 巴斯夫欧洲公司 | Method for producing 4-pentenoic acid |
JP2013502398A (en) * | 2009-08-21 | 2013-01-24 | ビーエーエスエフ ソシエタス・ヨーロピア | 4-pentenoic acid production method |
US8362296B2 (en) | 2009-08-21 | 2013-01-29 | Basf Se | Process for preparing 4-pentenoic acid |
Also Published As
Publication number | Publication date |
---|---|
NL93607C (en) | 1900-01-01 |
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