CN116023249A - Method for preparing carboxylic acid from isoamylene - Google Patents
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Abstract
The invention provides a method for preparing carboxylic acid from isoamylene, which comprises the following steps: the method comprises the steps of subjecting isoamylene and water to hydrocarboxylation reaction in CO under the action of a catalyst to obtain carboxylic acid, wherein the catalyst is selected from acid or a combination of acid, transition metal palladium complex and organic phosphine ligand. In the process of preparing carboxylic acid from isoamylene, under the acid catalysis condition, the conversion rate of isoamylene is 90-99%, and the selectivity of the product 2, 2-dimethylbutyric acid is 73-95%; under the catalysis of acid/palladium/organic phosphine ligand, the isoamylene conversion rate is 32-99%, and the selectivity of the 3-methyl valeric acid product is 25-95%. Compared with the prior reported multi-step synthesis method, the method can obtain the required high-added-value chemicals by a one-step method; the separation and purification steps are simple to operate, and the product purity is high.
Description
Technical Field
The invention relates to the technical field of efficient synthesis of carboxylic acid by using isoamylene, in particular to a method for preparing carboxylic acid by using isoamylene.
Background
Carbonylation is the reaction of olefins (or halogenated hydrocarbons) with carbon monoxide, different nucleophiles to synthesize aldehydes, carboxylic acids, esters, amides and other high value-added chemicals. When water is used as the nucleophile, the reaction to form the carboxylic acid under the influence of a transition metal (or acid) catalyst is referred to as a hydrocarboxylation reaction. The organic carboxylic acid compound (linear carboxylic acid or branched carboxylic acid) produced by the reaction can be widely applied to the production of medical intermediates, food industry or materials, and can be used as an intermediate for synthetic rubber, resin and organic synthesis, and also can be used as an admixture for improving the octane number of gasoline.
2, 2-dimethylbutyric acid is an important chemical industry, as well as pharmaceutical, pesticidal intermediates and lubricants, and downstream thereof can be used for preparing important chemicals such as 2, 2-dimethylbutyryl chloride, simvastatin, spirodiclofen and the like. 3-methyl valeric acid can be used as food additive due to slight faint scent, and is also a characteristic fragrance component of spice tobacco leaves; and is also widely applied to raw materials for synthesizing medicines and electronic liquid crystal directions.
The following problems exist in the synthesis of the above two carboxylic acids: 1) The traditional process has low yield, the purity of the product is difficult to purify due to inclusion of an extractant or a solvent, the purity is generally 96%, and the purity required in the actual use process is 99% or more; 2) The synthesis steps are complicated, and at least 2 steps are needed to obtain a target product; 3) The control of temperature and time in multi-step reactions is problematic and can have an important impact on yield; 4) The synthesis of target products by the one-step process of the isopentenyl carbonylation strategy is rarely reported in the existing literature and patents. Therefore, how to improve the one-step high-efficiency synthesis of 2, 2-dimethylbutyric acid and 3-methylpentanoic acid in the prior art route is important.
Disclosure of Invention
The technical problem solved by the invention is to provide a method for preparing carboxylic acid from isoamylene, which can be used for efficiently synthesizing 2, 2-dimethylbutyric acid under an acidic condition and synthesizing 3-methylpentanoic acid under an acidic condition and a transition metal palladium complex.
In view of this, the present application provides a process for preparing carboxylic acids from isoamylenes comprising:
the method comprises the steps of subjecting isoamylene and water to hydrocarboxylation reaction in CO under the action of a catalyst to obtain carboxylic acid, wherein the catalyst is selected from acid or a combination of acid, transition metal palladium complex and organic phosphine ligand.
Preferably, the acid is selected from one or more of sulfuric acid, phosphoric acid, hydrochloric acid, hydrofluoric acid, lewis acid and solid acid, and the acid is an aqueous solution of the acid, and the concentration is 30-90 wt%.
Preferably, the transition metal palladium complex is selected from one or more of palladium acetate, palladium dichloride, palladium acetylacetonate, palladium dichlorodiacetonitrile, palladium dichlorodibenzonitrile, palladium/carbon and tetrakis (triphenylphosphine) palladium, and the molar ratio of the transition metal palladium complex to the isoamylene is 1:50000-1:10.
Preferably, the organic phosphine ligand is selected from one or more of organic phosphine ligands shown in a formula (I) and an organic phosphine ligand shown in a formula (II);
wherein R is 1 ～R 2 Each independently selected from alkyl or aryl.
Preferably, the organophosphine ligand is selected from one or more of tri-n-butyl phosphine, tri-n-butyl phosphite, triphenylphosphine oxide, 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene, 1, 4-bis (diphenylphosphine) butane, 1 '-binaphthyl-2, 2' -bis-diphenylphosphine, bis (2-diphenylphosphinophenyl) ether.
Preferably, the molar ratio of the organic phosphine ligand to the transition metal palladium complex is 1:1-200:1.
Preferably, the reaction further comprises a solvent selected from one or more of n-hexane, n-pentane, tetrahydrofuran and water.
Preferably, the isoamylene is a mixture of 2-methyl-2-butene and 2-methyl-1-butene.
Preferably, the temperature of the reaction is 25-250 ℃ and the time is 1-48 h.
Preferably, the pressure of the CO is 0.1-20.0 MPa.
The application provides a method for preparing carboxylic acid from isoamylene, which comprises the following steps: the method comprises the steps of subjecting isoamylene and water to hydrocarboxylation reaction in CO under the action of a catalyst to obtain carboxylic acid, wherein the catalyst is selected from acid or a combination of acid, transition metal palladium complex and organic phosphine ligand. According to the preparation method of carboxylic acid, under the acidic condition, a transition metal catalyst is not introduced, and isoamylene can be efficiently converted into 2, 2-dimethylbutyric acid; 3-methyl valeric acid can be efficiently synthesized by introducing acid, transition metal palladium complex and organic phosphine ligand; therefore, the preparation method can synthesize the required chemicals more efficiently and with high selectivity through the regulation of the catalyst system; the yield of 2, 2-dimethylbutyric acid and 3-methylpentanoic acid produced by the traditional process is not high, the purity of the product is difficult to purify due to the inclusion of an extractant or a solvent, and the purity of the product carboxylic acid synthesized by the method can reach more than 98 percent; furthermore, the two carboxylic acids obtained by the hydrocarboxylation reaction can be widely applied to the production of medical intermediates, food industry or materials and the like; can be used as synthetic rubber, resin and organic synthesized intermediate, can be used as admixture for improving gasoline octane number and can be used as food additive or characteristic aroma component of spice tobacco leaf. In addition, the existing synthesis of the target product has complicated steps, at least two steps are needed to obtain the product, and the control of temperature and time in the multi-step reaction is problematic, so that the yield is greatly affected; the method provided by the application can be used for efficiently synthesizing the target product by a one-step method, and has the advantages of simple steps and easy separation of the products.
Drawings
FIG. 1 is a GC diagram of 2, 2-dimethylbutyric acid produced in example 1 of the present invention;
FIG. 2 is a hydrogen spectrum of 2, 2-dimethylbutyric acid prepared in example 1 of the present invention;
FIG. 3 is a carbon spectrum of 2, 2-dimethylbutyric acid produced in example 1 of the present invention;
FIG. 4 is a GC diagram of 3-methylpentanoic acid prepared in example 10 of the present invention;
FIG. 5 is a hydrogen spectrum of 3-methylpentanoic acid prepared in example 10 of the present invention;
FIG. 6 is a carbon spectrum of 3-methylpentanoic acid prepared in example 10 of the present invention.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
In view of the demand of efficient synthesis of 2, 2-dimethylbutyric acid and 3-methylpentanoic acid by olefin in the prior art, the application provides a method for efficiently synthesizing 2, 2-dimethylbutyric acid or 3-methylpentanoic acid by hydrocarboxylation reaction of isoamylene under an acidic condition, particularly, under the acidic condition, the 2, 2-dimethylbutyric acid can be efficiently synthesized without adding a transition metal catalyst, and under the condition of acid and a transition metal palladium complex, the 3-methylpentanoic acid can be efficiently synthesized. Specifically, the embodiment of the invention discloses a method for preparing carboxylic acid from isoamylene, which comprises the following steps:
the method comprises the steps of subjecting isoamylene and water to hydrocarboxylation reaction in CO under the action of a catalyst to obtain carboxylic acid, wherein the catalyst is selected from acid or a combination of acid, transition metal palladium complex and organic phosphine ligand.
In the preparation method, the isoamylene can be efficiently converted into the 2, 2-dimethylbutyric acid under the acidic condition without introducing a transition metal palladium complex, and in the process, the acid is specifically acid dissolved into waterThe concentration of the acid solution is 10 to 90 percent by weight; the acid is selected from sulfuric acid, phosphoric acid, hydrochloric acid, hydrofluoric acid, lewis acid (BF) 3 ) And one or more of solid acids, specifically, the concentration of the sulfuric acid is 90wt%, the concentrations of the hydrochloric acid, the hydrofluoric acid and the boron trifluoride are 30wt%, and the concentration of the phosphoric acid is 80wt%; in this application, the acid is selected from 90wt% sulfuric acid.
Under the condition of adding acid and transition metal palladium complex, the isoamylene can efficiently synthesize 3-methyl valeric acid; in this preparation, the catalytic system comprises an acid, a transition metal palladium complex and an organophosphine ligand; the acid is specifically an acid solution in which the acid is dissolved into water, and the concentration of the acid is 10-90 wt%; the acid is selected from sulfuric acid, phosphoric acid, hydrochloric acid, hydrofluoric acid, lewis acid (BF) 3 ) And one or more of solid acids, specifically, the concentration of the sulfuric acid is 90wt%, the concentrations of the hydrochloric acid, the hydrofluoric acid and the boron trifluoride are 30wt%, the concentration of the phosphoric acid is 80wt%, and in this application, the acid is selected from 90wt% sulfuric acid. The transition metal palladium complex is selected from palladium acetate (Pd (OAc) 2 ) Palladium dichloride (PdCl) 2 ) Palladium acetylacetonate (Pd (acac)) 2 ) Palladium dichlorodiacetonitrile (Pd (CH) 3 CN) 2 Cl 2 ) Palladium dichloro dibenzonitrile (Pd (PhCN) 2 Cl 2 ) Palladium on carbon (Pd/C) and tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The molar ratio of the transition metal palladium complex to the isoamylene is 1:50000-1:10; specifically, the transition metal palladium complex is selected from palladium acetate, and the molar ratio of the transition metal palladium complex to the isoamylene is 1:10000-1:1000, more specifically 1:5000. The organic phosphine ligand is selected from one or more of organic phosphine ligands shown in a formula (I) and an organic phosphine ligand shown in a formula (II);
wherein R is 1 ～R 2 Each independently selected from alkyl or aryl.
More specifically, the organophosphine ligand is selected from tri-n-butylphosphine (P (nBu) 3 ) Tri-n-butyl phosphite (P (O-nBu) 3 ) Triphenylphosphine (PPh) 3 ) Triphenylphosphine oxide (o=pph) 3 ) 4, 5-Didiphenylphosphine-9, 9-dimethylxanthenes (Xantphos), 1, 4-bis (diphenylphosphine) butane (DPPB), 1 '-binaphthyl-2, 2' -Bisdiphenylphosphine (BINAP), bis (2-diphenylphosphinophenyl) ether (DPEPhos), the most preferred organophosphine ligand being triphenylphosphine (PPh) 3 ) The method comprises the steps of carrying out a first treatment on the surface of the The structure of the above-mentioned organic phosphine ligand is specifically shown below; the source of the organophosphine ligand is not particularly limited, and may be prepared according to a method well known to those skilled in the art, or may be commercially available;
in the above-mentioned catalytic system, the molar ratio of the organophosphine ligand to the transition metal palladium complex is 1:1 to 200:1, specifically, the molar ratio of the organophosphine ligand to the transition metal palladium complex is 1:1 to 50:1, more specifically, 10:1.
In the process of preparing carboxylic acid, the solvent can be added, wherein the solvent can be one or more selected from n-hexane, n-pentane, tetrahydrofuran and water, and particularly the solvent is selected from n-hexane. The temperature of the reaction is 25-250 ℃, specifically 50-150 ℃, more specifically 100 ℃; the reaction time is 1 to 48 hours, specifically 5 to 15 hours, more specifically 10 hours. The pressure of the CO (CO) in the hydrocarboxylation reaction is 0.1-20.0 MPa, specifically 1.0-5.0 MPa, and more specifically 2.0MPa.
In the present application, the isoamylene is a mixture of 2-methyl-2-butene and 2-methyl-1-butene, and the molar ratio of the two is not limited, specifically, the isoamylene is 2-methyl-2-butene and 2-methyl-1-butene with a molar ratio of 90:10.
The method for preparing carboxylic acid from isoamylene specifically comprises the following steps: adding acid or palladium catalyst, phosphine ligand, acid catalyst system, isoamylene and water in certain concentration into a reaction bottle, putting the reaction bottle into a high-pressure reaction kettle, filling CO into the reaction kettle for three times to clean air in the reaction kettle, and filling CO to 0.1-20.0 MPa; placing the autoclave in a constant temperature oil bath for reaction, after the reaction is finished, placing the autoclave in ice water for cooling to room temperature, transferring the reaction liquid to a 2mL glass bottle by using a rubber head dropper, determining the substrate conversion rate and the product selectivity by gas chromatography, and then performing reduced pressure distillation to obtain 2, 2-dimethylbutyric acid or 3-methylpentanoic acid; during the experiment, when the carbon monoxide pressure is less than 1.0MPa, the pressure is supplemented to 2.0MPa.
Experimental results show that under the acid catalysis condition, the conversion rate of isoamylene is 90-99%, and the selectivity of the product 2, 2-dimethylbutyric acid is 73-95%; under the catalysis of acid/palladium/organic phosphine ligand, the isoamylene conversion rate is 32-99%, and the selectivity of the product 3-methyl valeric acid is 25-95%.
In order to further understand the present invention, the following examples are provided to illustrate the method for preparing carboxylic acid from isoamylene, and the scope of the present invention is not limited by the following examples.
Examples 1 to 5
The method for efficiently preparing the 2, 2-dimethylbutyric acid by catalyzing the hydrogen carboxylation reaction of the isoamylene by different acids comprises the following operation steps:
sequentially adding 150mmol of an acid catalyst, 100mmol of isoamylene, 200mmol of water and 100mL of n-hexane into a reaction bottle, putting the reaction bottle into a high-pressure reaction kettle, filling and discharging CO of 0.2MPa into the high-pressure reaction kettle for three times to clean the reaction kettle, filling CO into the high-pressure reaction kettle to 2.0MPa, putting the high-pressure reaction kettle into a constant-temperature oil bath kettle, reacting for 10 hours at the temperature of 100 ℃, and determining the substrate conversion rate and the product selectivity through gas chromatography analysis after the reaction is finished; the nuclear magnetic characterization structure of the high-purity product is obtained through reduced pressure distillation and separation, and the nuclear magnetic spectrum and GC purity are shown in figures 1-3, which are the nuclear magnetic spectrum and GC purity curve chart of the 2, 2-dimethylbutyric acid prepared in example 1; as can be seen from FIG. 1, the purity of the product was 99.7%, and the data in FIGS. 2 and 3 were 1 H NMR(400MHz,Chloroform-d)δ12.11(s,1H),1.60(q,J＝7.5Hz,2H),1.18(s,6H),0.89(t,J＝7.5Hz,3H)； 13 C NMR (101 MHz, chlorine-d). Delta. 185.31,42.48,33.11,24.37,9.14. The reaction process is as followsThe formula is shown as follows:
table 1 provides experimental results of the catalytic carboxylation of isoamylene to 2, 2-dimethylbutyric acid using different acid catalysts;
TABLE 1 data table for synthesizing 2, 2-dimethylbutyric acid by acid catalyzed hydrocarboxylation of isoamylenes a
| Examples | Acid(s) | Isoamylene conversion (%) b | Yield of 2, 2-dimethylbutyric acid B (%) b |
| 1 | |
99 | 95 |
| 2 | Phosphoric acid | 97 | 85 |
| 3 | |
99 | 73 |
| 4 | Hydrofluoric acid | 93 | 90 |
| 5 | Boron trifluoride | 90 | 91 |
In the table, a represents 100.0mmol of isopentene, 150.0mmol of 90% sulfuric acid (wherein, hydrochloric acid, hydrofluoric acid and boron trifluoride are 30% aqueous solutions, and phosphoric acid is 80% aqueous solutions), 200.0mmol of water, 100mL of n-hexane, 2.0MPa of CO2, 100 ℃ for 10 hours; b represents gas chromatographic analysis, n-dodecane is used as internal standard.
Examples 6 to 9
The preparation method comprises the following steps of efficiently preparing 2, 2-dimethylbutyric acid by catalyzing the hydrogen carboxylation reaction of isoamylene with concentrated sulfuric acid under different solvents:
sequentially adding 150mmol of 90% sulfuric acid catalyst, 100mmol of isoamylene, 200mmol of water and 100mL of solvent into a reaction bottle, putting the reaction bottle into a high-pressure reaction kettle, filling and discharging CO of 0.2MPa into the high-pressure reaction kettle for three times to clean the reaction kettle, filling CO into the high-pressure reaction kettle to 2.0MPa, putting the high-pressure reaction kettle into a constant-temperature oil bath kettle, reacting for 10 hours at the temperature of 100 ℃, and determining the substrate conversion rate and the product selectivity through gas chromatography after the reaction is finished. The reaction process is specifically shown as the following formula:
table 2 provides experimental results of sulfuric acid catalyzed hydrocarboxylation of isoamylene to 2, 2-dimethylbutyric acid under different solvent conditions;
TABLE 2 data table for synthesizing 2, 2-dimethylbutyric acid by sulfuric acid catalyzed hydrocarboxylation of isoamylene in different solvent conditions a
| Examples | Solvent(s) | Isoamylene conversion (%) b | Yield of 2, 2-dimethylbutyric acid B (%) b |
| 6 | Without any means for | 99 | 93 |
| 7 | Cyclopentane process | 98 | 83 |
| 8 | Tetrahydrofuran (THF) | 95 | 79 |
| 9 | Water and its |
90 | 90 |
In the table, a represents 100.0mmol of isoamylene, 150.0mmol of 90% sulfuric acid, 200.0mmol of water, 100mL of solvent, 2.0MPa of CO2, 100℃for 10 hours, and b represents gas chromatography analysis, n-dodecane being used as an internal standard.
Examples 10 to 16
Different palladium complexes participate in acid/palladium/organic phosphine ligand to catalyze the hydrogen carboxylation reaction of isopentene to prepare 3-methyl valeric acid with high efficiency, and the operation steps are as follows:
sequentially adding 0.02mmol of palladium catalyst, 0.2mmol of triphenylphosphine, 100mmol of 90% sulfuric acid, 100mmol of isoamylene, 200mmol of water and 100mL of normal hexane into a reaction bottle, putting the reaction bottle into a high-pressure reaction kettle, filling CO of 0.2MPa into the reaction kettle for three times to clean the reaction kettle, filling CO to 2.0MPa, putting the high-pressure kettle into a constant-temperature oil bath kettle, reacting for 10 hours at the temperature of 100 ℃, and determining the substrate conversion rate and the product selectivity through gas chromatography analysis after the reaction is finished; the nuclear magnetic characterization structure of the high-purity product is obtained through reduced pressure distillation and separation, and the nuclear magnetic spectrum and GC purity are shown in figures 4-6, which are the nuclear magnetic spectrum and GC purity curve chart of the 3-methyl valeric acid prepared in example 10; as can be seen from FIG. 4, the purity of 3-methylpentanoic acid was 99.9%, and the data in FIGS. 5 and 6 were that 1 H NMR(400MHz,Chloroform-d)δ11.56(s,1H),2.36(dd,J＝15.0,6.1Hz,1H),2.15(dd,J＝14.9,8.1Hz,1H),1.96–1.81(m,1H),1.46–1.19(m,2H),1.08–0.76(m,6H)； 13 C NMR (101 MHz, chlorine-d). Delta. 180.27,41.26,31.70,29.25,19.18,11.21. The reaction process is shown as follows:
table 3 provides experimental results of the efficient preparation of 3-methylpentanoic acid from different palladium complexes involved in the acid/palladium/organophosphine ligand catalyzed hydrocarboxylation of isopentene;
TABLE 3 data table of results of different palladium complexes involved in "acid/palladium/organophosphine ligand" catalyzed hydrocarboxylation of isoamylene to efficiently prepare 3-methylpentanoic acid a
| Examples | Palladium catalyst | Isoamylene conversion (%) b | Yield of 3-methylpentanoic acid C (%) b |
| 10 | |
99 | 95 |
| 11 | |
99 | 94 |
| 12 | Palladium acetylacetonate | 98 | 90 |
| 13 | |
90 | 80 |
| 14 | |
90 | 82 |
| 15 | Palladium on carbon | 32 | 25 |
| 16 | Tetrakis (triphenylphosphine) |
99 | 92 |
In the table, a represents 0.02mmol of palladium catalyst, 0.2mmol of triphenylphosphine, 100.0mmol of isoamylene, 100.0mmol of 90% sulfuric acid, 200.0mmol of water, 100mL of n-hexane, CO2.0MPa,100℃for 10 hours, and b represents gas chromatography analysis, n-dodecane being used as an internal standard.
Examples 17 to 23
Different organic phosphine ligands participate in 'sulfuric acid/palladium acetate/organic phosphine ligand' to catalyze the hydrogen carboxylation reaction of isopentene to prepare 3-methyl valeric acid with high efficiency, and the operation steps are as follows:
adding 0.02mmol of palladium acetate, 0.2mmol of organic phosphine ligand, 100mmol of 90% sulfuric acid, 100mmol of isoamylene, 200mmol of water and 100mL of normal hexane into a reaction bottle in sequence, putting the reaction bottle into a high-pressure reaction kettle, filling CO of 0.2MPa into the reaction kettle for three times to clean the reaction kettle, filling CO to 2.0MPa, putting the high-pressure kettle into a constant-temperature oil bath kettle, reacting for 10 hours at the temperature of 100 ℃, and determining the substrate conversion rate and the product selectivity through gas chromatography analysis after the reaction is finished. The reaction process is specifically shown in the following formula;
table 4 provides experimental results of the efficient preparation of 3-methylpentanoic acid from different organophosphine ligands participating in the "sulfuric acid/palladium acetate/organophosphine ligand" catalyzed hydrocarboxylation of isoamylene.
TABLE 4 efficient preparation of 3-methylpentanoic acid with different organophosphine ligands involved in "sulfuric acid/Palladium acetate/organophosphine ligand" catalyzed hydrocarboxylation of Isopentenyl a
| Examples | Organic phosphine ligands | Isoamylene conversion (%) b | Yield of 3-methylpentanoic acid C (%) b |
| 17 | P(nBu) 3 | 85 | 75 |
| 18 | P(O-nBu) 3 | 90 | 80 |
| 19 | O＝PPh 3 | 88 | 79 |
| 20 | Xantphos | 98 | 78 |
| 21 | DPPB | 99 | 80 |
| 22 | BINAP | 95 | 88 |
| 23 | |
90 | 86 |
In the table, a represents Pd (OAc) 2 0.02mmol of organic phosphine ligand, 0.2mmol of isoamylene, 100.0mmol of 90% sulfuric acid, 200.0mmol of water, 100mL of n-hexane, 2.0MPa of CO2, 100 ℃ for 10 hours; b represents gas chromatographic analysis, n-dodecane is used as internal standard.
Examples 24 to 27
Different solvents participate in sulfuric acid/palladium acetate/triphenylphosphine catalytic isoamylene hydrocarboxylation reaction to efficiently prepare 3-methyl valeric acid, and the operation steps are as follows:
adding 0.02mmol of palladium acetate, 0.2mmol of triphenylphosphine, 100mmol of 90% sulfuric acid, 100mmol of isoamylene, 200mmol of water and 100mL of solvent into a reaction bottle in sequence, putting the reaction bottle into a high-pressure reaction kettle, filling and discharging CO of 0.2MPa into the high-pressure reaction kettle for three times to clean the reaction kettle, filling CO to 2.0MPa, putting the high-pressure reaction kettle into a constant-temperature oil bath kettle, reacting for 10 hours at the temperature of 100 ℃, and determining the substrate conversion rate and the product selectivity through gas chromatography after the reaction is finished. The reaction process is specifically shown in the following formula;
table 5 shows the experimental results of the efficient preparation of 3-methylpentanoic acid by the participation of different solvents in the sulfuric acid/palladium acetate/triphenylphosphine catalyzed hydrocarboxylation reaction of isopentene;
TABLE 5 efficient preparation of 3-methylpentanoic acid data table with different solvents participating in "sulfuric acid/palladium acetate/triphenylphosphine" catalyzed hydrocarboxylation of isoamylene a
| Examples | Solvent(s) | Isoamylene conversion (%) b | Yield of 3-methylpentanoic acid C (%) b |
| 24 | Without any means for | 99 | 90 |
| 25 | Cyclopentane process | 97 | 79 |
| 26 | Tetrahydrofuran (THF) | 93 | 81 |
| 27 | Water and its preparation method | 92 | 90 |
In the table, a represents Pd (OAc) 2 0.02mmol, triphenylphosphine 0.2mmol, isoamylene 100.0mmol,90% sulfuric acid 100.0mmol, water 200.0mmol, solvent 100mL, CO2.0MPa, 100deg.C for 10 hr; b represents gas chromatographic analysis, n-dodecane is used as internal standard.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A process for preparing carboxylic acids from isoamylenes comprising:
the method comprises the steps of subjecting isoamylene and water to hydrocarboxylation reaction in CO under the action of a catalyst to obtain carboxylic acid, wherein the catalyst is selected from acid or a combination of acid, transition metal palladium complex and organic phosphine ligand.
2. The method of claim 1, wherein the acid is selected from one or more of sulfuric acid, phosphoric acid, hydrochloric acid, hydrofluoric acid, lewis acid, and solid acid, and the acid is an aqueous acid solution having a concentration of 30 to 90wt%.
3. The method according to claim 1, wherein the transition metal palladium complex is selected from one or more of palladium acetate, palladium dichloride, palladium acetylacetonate, palladium dichlorodiacetonitrile, palladium dichlorodibenzonitrile, palladium on carbon and tetrakis (triphenylphosphine) palladium, and the molar ratio of the transition metal palladium complex to the isopentene is 1:50000-1:10.
4. The method according to claim 1, wherein the organophosphine ligand is selected from one or more of the organophosphine ligands shown in formula (i) and formula (ii);
wherein R is 1 ～R 2 Each independently selected from alkyl or aryl.
5. The process according to claim 1 or 4, wherein the organophosphine ligand is selected from one or more of tri-n-butylphosphine, tri-n-butylphosphite, triphenylphosphine oxide, 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene, 1, 4-bis (diphenylphosphine) butane, 1 '-binaphthyl-2, 2' -bis-diphenylphosphine, bis (2-diphenylphosphinophenyl) ether.
6. The method according to claim 1, wherein the molar ratio of the organophosphine ligand and the transition metal palladium complex is from 1:1 to 200:1.
7. The method of claim 1, wherein the reaction further comprises a solvent selected from one or more of n-hexane, n-pentane, tetrahydrofuran, and water.
8. The method of claim 1, wherein the isoamylene is a mixture of 2-methyl-2-butene and 2-methyl-1-butene.
9. The method according to claim 1, wherein the reaction is carried out at a temperature of 25 to 250 ℃ for a time of 1 to 48 hours.
10. The method according to claim 1, wherein the pressure of the CO is 0.1 to 20.0MPa.
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