MXPA98002953A - Procedure for the preparation of dedi-terbut succinate - Google Patents
Procedure for the preparation of dedi-terbut succinateInfo
- Publication number
- MXPA98002953A MXPA98002953A MXPA/A/1998/002953A MX9802953A MXPA98002953A MX PA98002953 A MXPA98002953 A MX PA98002953A MX 9802953 A MX9802953 A MX 9802953A MX PA98002953 A MXPA98002953 A MX PA98002953A
- Authority
- MX
- Mexico
- Prior art keywords
- succinic acid
- acid
- isobutene
- weight
- esterification
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229940086735 succinate Drugs 0.000 title claims 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 title claims 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 52
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000001384 succinic acid Substances 0.000 claims abstract description 26
- VQTUBCCKSQIDNK-UHFFFAOYSA-N isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 18
- RINCXYDBBGOEEQ-UHFFFAOYSA-N Succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005886 esterification reaction Methods 0.000 claims abstract description 16
- GOORECODRBZTKF-UHFFFAOYSA-N ditert-butyl butanedioate Chemical compound CC(C)(C)OC(=O)CCC(=O)OC(C)(C)C GOORECODRBZTKF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 150000003460 sulfonic acids Chemical class 0.000 claims description 2
- QKWILNTYPDJSME-UHFFFAOYSA-N pyrrolo[3,4-c]pyrrole-3,6-dione Chemical compound C1=NC(=O)C2=C1C(=O)N=C2 QKWILNTYPDJSME-UHFFFAOYSA-N 0.000 claims 1
- 230000000875 corresponding Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 239000012074 organic phase Substances 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000006184 cosolvent Substances 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N t-BuOH Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- 239000012043 crude product Substances 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000012258 stirred mixture Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- -1 for example Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-Dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N Octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- CHDFNIZLAAFFPX-UHFFFAOYSA-N ethoxyethane;oxolane Chemical compound CCOCC.C1CCOC1 CHDFNIZLAAFFPX-UHFFFAOYSA-N 0.000 description 1
- 239000008079 hexane Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011031 large scale production Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000003449 preventive Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Abstract
A process for the preparation of di-tert-butyl succinate of the formula (I) is described, by means of proton-catalyzed esterification of succinic acid with isobutene, which comprises reacting succinic acid or succinic acid anhydride, or mixtures thereof , with isobutene in the presence of an acid esterification catalyst containing water, provided that the sulfuric acid is used in a concentration not greater than 65% by weight. Through this process it is possible to prepare di-tert-butyl succinate by reacting succinic acid or succinic acid anhydride, or corresponding mixtures of succinic acid and succinic acid anhydride, with isobutene with a reduced heat evolution and, at the same time, a production increased and an improved purity of the end product
Description
PROCEDURE FOR THE PREPARATION OF DILOR-BUTYL SUCCINATE
DESCRIPTION OF THE INVENTION
The present invention relates to a novel process for the preparation of di-tert-butyl succinate of the formula:
through the proton-catalyzed esterification of succinic acid with isobutene. The preparation of ter-alkylate from carboxylic acids with alkenes in the presence of a concentrated acid, either with or without the addition of aprotic organic cosolvents, such as diethyl ether or dioxane (AL McCloskey and GS Fonken, Org. Synth. Coil Vol. 4, 261 (1963)), is known. Esterification of succinic acid with isobutene in the presence of concentrated sulfuric acid and tert-butanol as a protic cosolvent is further described by H. Pielartzik, B. Irmisch-Piellartzik, T. Eicher in Houben-Weyl, Vol. E5 / 1, p. 662 et seq. (1985). A disadvantage for the technical application of this procedure is the high heat evolution during the addition of concentrated sulfuric acid, which is very difficult to control, especially in large-scale production, and which results in safety hazards, as well as considerable variations in production and quality. Isobutene polymerization products are formed, for example, the separation of which from di-tert-butyl succinate is difficult and, therefore, economically disadvantageous. In addition, the necessary work is a consumer of time, work and energy. Preventive measures to control the heat, which is released, require cooling systems that involve a complicated apparatus and a correspondingly slow flow rate of sulfuric acid. The infrastructure, the long reaction time and the poor reproducibility resulting from the process are economically disadvantageous. The object of this invention is, therefore, to overcome the above disadvantages and provide a robust and stable procedure, which is economically attractive. Accordingly, this invention relates to an improved process for the preparation of di-tert-butyl succinate of the formula:
(I), through proton-catalyzed esterification of succinic acid with isobutene, which comprises reacting succinic acid or succinic acid anhydride, or mixtures thereof, with isobutene, in the presence of an acid esterification catalyst containing water, provided that the sulfuric acid is used in a concentration not greater than 95% by weight. The molar ratio of the succinic acid or succinic acid anhydride, or mixtures thereof, to isobutene is usually selected in the range of 1: 2 to 1: 50, preferably 1: 6 to 1: 13.
The molar ratio of succinic acid to succinic acid anhydride in the mixture is usually selected in the range of 1: 100 to 100: 1, preferably 8: 2 to 2: 8 and, particularly preferably, 1: 1. In accordance with this invention, esterification catalysts containing water are used, provided that the sulfuric acid is used in a concentration of not more than 95% by weight. Usually, from 40 to 90, preferably from 40 to 80, and particularly preferably from 50 to 75% by weight, of aqueous mineral acids, for example, sulfuric acid, phosphoric acid or organic sulfonic acids, such as methanesulfonic acid are used. . When succinic acid is used, it is preferred to use from 65 to 75% by weight of the aqueous sulfuric acid, when using succinic acid anhydride, from 55 to 65% by weight of aqueous sulfuric acid. Usually from 0.1 to 1 .3 moles of esterification catalyst is used per mole of succinic acid or succinic acid anhydride, or a mixture thereof. It is particularly preferred to use 0.5 to 0.8 moles of sulfuric acid per mole of succinic acid or succinic acid anhydride. The esterification is usually carried out at a temperature range of 263 to 333 ° K and at a pressure of on the scale of (1 x 10s) to (25 x 105) Pa. The reaction temperature is preferably on the scale of 283. at 313 ° K to (2 x 10s) to (8 x 105) Pa, particularly most preferably from 293 to 303 ° K, the reaction mixture in the latter case preferably being maintained at a pressure in the range of (3 x 105) to (6 x 10s) Pa. The reaction is preferably carried to without cosolvents or organic solvents, but it is also possible to carry out the reaction with them. The choice and quantity of organic solvents or cosolvents depends on the preferred scale and is usually in the range of 0.01 to 50% by weight, preferably in the range of 0.01 to 0% by weight and, particularly preferably, in the scale from 0.01 to 10% by weight, based on isobutene. Organic solvents and cosolvents are, for example, aprotic organic solvents, such as orthodichlorobenzene, or aliphatic hydrocarbons, typically hexane, octane, or ligroin, or ethers, for example, dioxane, tetrahydrofuran or diethyl ether, or protic solvents, such as ter-alcohols, preferably ter-butanolic or ter-amyl alcohol. The advantages of the novel processes are that the esterification proceeds with a considerably low heat evolution, a high production of a markedly less impure crude product, which is obtained at the same time. This makes unnecessary elaborate purification procedures, which are required when using di-tert-butyl succinate as a starting material for the preparation of 1,4-diketo-pyrrolo- [3,4-c] pigments -pyrrol. The invention is illustrated through the following examples:
EXAMPLE 1 (Aqueous sulfuric acid / Etc .: Succinic acid)
An autoclave was charged with 212.5 g (1.80 moles) of succinic acid and then 935 g (16.65 moles) of isobutene were forced to a jacket temperature of 263 ° K. After the addition was complete, 146.4 g (1.08 mole) of 72.3% by weight of sulfuric acid were pumped for 45 minutes at a temperature of 268 to 275 ° K in the vessel. The reaction mixture was then stirred for 30 minutes at a temperature of 275 to 278 ° K in the vessel and, after increasing the temperature from 293 to 295 ° K, it was stirred for 14 hours at that temperature and at a pressure of (4). x 10 s) to (5 x 10 s) Pa. This reaction mixture was then forced into a stirred mixture consisting of 1000 g of ice and 300 ml (3 moles) and 30% by weight of a sodium hydroxide solution and the autoclave then it was flooded with 200-300 ml of petroleum ether, which was also added to the ice / sodium hydroxide solution mixture. The mixture was warmed to room temperature and the organic phase was separated. The aqueous phase was extracted 3 times with 100-150 ml of petroleum ether and the organic phases were then combined. The organic phases were concentrated in a rotary evaporator at a bath temperature of 323 ° K and a (3 x 103) Pa (final value). To purify the crude product, the outgoing vapors were distilled in the upper part, with the addition of approximately 0.5 g of magnesium oxide, through a packed column of 30 cm (Raschig rings 5 x 5 mm) under vacuum. This gives 358.2 g (86.4% theory) of di-tert-butyl succinate (eg: 0.8 - 0.9 Pa at 321 to 324 ° K) of 99.0% purity (percentage by area), determined through gas chromatography , corresponding to 85.6% theory to 100%. Evolution of heat during the addition of sulfuric acid: 26 KJ / mol, Total reaction heat: 108 KJ / mol of succinic acid.
EXAMPLE 2 (Comparison with the State of the Art in H. Pielartzik, B. Irmisch-Piellartzik, T. Eicher in Houben-Weyl, Vol. E5 / 1, page 662 et seq. (1985), where acid was used sulfuric and tert-butanol as cosolvent for the esterification of succinic acid with isobutene)
An autoclave was charged with 212.5 g (1.80 moles) of succinic acid and 166.8 g (2.25 moles) of tert-butanol and then 808 g (14.40 moles) of isobutene were forced at a walking temperature of 263 ° K. After the addition was complete, 108.1 g (1.08 mole) of 98% sulfuric acid was pumped for 70 minutes at a temperature of 268 to 275 ° K in the vessel. The reaction mixture was then stirred for 30 minutes at a temperature of 275 to 278 ° K in the vessel and, after increasing the temperature from 293 to 295 ° K, it was stirred for another 14 hours at that temperature and at a pressure of (4 x 105) a (5 x 10s) Pa. The reaction mixture was then forced into a stirred mixture consisting of 1000 g of ice and 300 ml (3 moles) of 30% of a sodium hydroxide solution and the autoclave was then flooded with 200-300 ml of petroleum ether, which was also added to the ice / sodium hydroxide solution mixture. The mixture was warmed to room temperature and the organic phase was separated. The aqueous phase was extracted 3 times with 100-150 ml of petroleum ether and the organic phases were combined. The organic phases were concentrated in a rotary evaporator at a bath temperature of 323 ° K and (3 x 103) Pa (final volume). To purify the crude product, it was distilled in fractionated form, with the addition of approximately 0.5 g of magnesium oxide, through a 30 cm packed column (5 x 5 mm Raschig rings) under vacuum. The ester content of the individual fractions was determined by gas chromatography. Fractions that have ester contents of < 97% by weight were distilled again. After a total of 3 distillations, 329.3 g (79.4% theory) of di-tert-butyl succinate having a purity of 97.2% (percentage per area), determined through gas chromatography, corresponding to 7.2, were obtained. % theory to 100% Evolution of heat during the addition of sulfuric acid: -77
KJ / moles, Total reaction heat: 120 KJ / moles of succinic acid.
EXAMPLE 3 (Etcid: Succinic acid anhydride)
An autoclave was charged with 190.2 g (1.90 mole) of succinic acid anhydride and then 986 g (17.58 mole) of isobutene were forced at a walking temperature of 263 ° K. After completion of the addition, 186.4 g (1 g) were pumped (1 g). .14 moles) of 60.0% sulfuric acid for 45 minutes at a temperature of 266 to 273 ° K in the vessel. The reaction mixture was then stirred for 30 minutes at a temperature of 273 to 278 ° K in the vessel and, after increasing the temperature from 293 to 295 ° K, it was stirred for another 14 hours at that temperature and at a pressure of (4 x 105) a (5 x 10s) Pa. The reaction mixture was then forced into a stirred mixture consisting of 1000 g of ice and 315 ml (3.15 mole) of 30% sodium hydroxide solution and the autoclave then it was flooded with 200-300 ml of petroleum ether, which was also added to the ice / sodium hydroxide solution mixture. The mixture was warmed to room temperature and the organic phase was separated. The aqueous phase was extracted 3 times with 100-150 ml of petroleum ether and the organic phases were combined. The organic phases were concentrated in a rotary evaporator at a bath temperature of 323 ° K and (3 x 103) Pa (final volume). To purify the crude product, the outgoing vapors were distilled at the top, with the addition of approximately 0.5 g of magnesium oxide, through a 30 cm packed column (5 x 5 mm Raschig rings) under vacuum. This gave 385.0 g (88.0% theory) of di-tert-butyl succinate (eg: 0.4 - 0.6 Pa of 320 to 323 ° K) of 99.6% purity (percentage per area), determined through chromatography, which corresponds to 87.6% theory to 100%. Evolution of heat during the addition of sulfuric acid: -23 KJ / mol, Total reaction heat: 145 KJ / mol of succinic acid anhydride.
EXAMPLE 4 (High Reaction Temperature + Shortest Reaction Time)
An autoclave was charged with 212.5 g (1.80 moles) of succinic acid and then 943 g (16.81 moles) of isobutene were forced to a jacket temperature of 273 ° K. After the addition was complete, 149.2 g (1.08 mole) of 71.0% by weight of sulfuric acid were pumped for 45 minutes at a temperature of 275 to 283 ° K in the vessel. The jacket temperature was then increased to approximately 298 ° K and the reaction mixture was stirred for 7 hours at a temperature of 298 + 0.5 ° K in the vessel at a pressure of (3 x 105) to (5 x 105) Pa This reaction mixture was forced to a stirred mixture consisting of 500 g of ice, 500 g of water and 300 ml (3 mols) of 30% of a sodium hydroxide solution and the autoclave was then flooded with 200-300 ml. of petroleum ether, which was also added to the ice / water / sodium hydroxide solution mixture. The mixture was warmed to room temperature and the organic phase was separated. The aqueous phase was extracted 3 times with 100-150 ml of petroleum ether and the organic phases were then combined. The organic phases were concentrated in a rotary evaporator at a bath temperature of 323 ° K and (3 x 103) Pa (final volume). To purify the crude product, the outgoing vapors were distilled at the top, with the addition of approximately 0.5 g of magnesium oxide, through a 30 cm packed column (5 x 5 mm Raschig rings) under vacuum. This gave 360.7 g (87.0% theory) of di-tert-butyl succinate (eg: 0.8 - 0.9 Pa from 321 to 324 ° K) of 99.4% purity (percentage by area), determined through chromatography, which corresponds to 86.5% theory to 100%.
Claims (5)
1. - A process for the preparation of a di-tert-butyl succinate of the formula: through succinate catalyzed esterification of succinic acid with isobutene, which comprises reacting succinic acid or succinic acid anhydride, or mixtures thereof, with isobutene in the presence of an acid esterification catalyst containing water, provided that the Sulfuric acid is used in a concentration not higher than 65% by weight.
2. A process according to claim 1, wherein the molar ratio of succinic acid or succinic acid anhydride, or mixtures thereof, to isobutene is from 1: 2 to 1:50.
3. A process according to claim 1, wherein the molar ratio of succinic acid to succinic acid anhydride in the mixture is in the range of 1: 100 to 100: 1.
4 - A process according to claim 1, wherein the acid esterification catalysts are from 40 to 90% by weight of aqueous sulfuric acid or phosphoric acid, or organic sulfonic acids, such as methanesulfonic acid.
5. - A process according to claim 1, which, when succinic acid is used, comprises using 65 to 75% by weight of aqueous sulfuric acid and, when succinic acid anhydride is used, of 55 to 65% by weight of acid aqueous sulfuric 6 - A process according to claim 1, which comprises using 0.1 to 1 .3 moles of esterification catalyst per mole of succinic acid or succinic acid anhydride or mixtures thereof. 7 - A method according to claim 1, which comprises the esterification on the temperature scale of 263 to 333 ° K and at a pressure of (1 x 10s) to (25 x 105) Pa. 8.- The use of the di-tert-butyl succinate of the formula (I) obtained by the process according to claim 1, for the preparation of 1,4-diketopyrrolo- [3,4-c] -pyrrole pigments.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH873/97 | 1997-04-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| MXPA98002953A true MXPA98002953A (en) | 1999-04-06 |
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