CN113336637B - Synthesis method of trans-2-methyl-2-pentenoic acid - Google Patents
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Abstract
The invention adopts a Reppe synthesis method to prepare the strawberry acid, and firstly takes piperylene, carbon monoxide and water as raw materials, and takes noble metal rhodium salt and organic phosphine ligand as catalysts to obtain cis-trans isomeric intermediates of 2-methyl-3-pentenoic acid, and then the trans-2-methyl-2-pentenoic acid, namely trans-strawberry acid, is generated by the isomerization reaction of the obtained intermediates.
Description
Technical Field
The invention relates to a reaction for synthesizing acid by using olefin as a raw material, in particular to a method for synthesizing trans-2-methyl-2-pentenoic acid, belonging to the fields of fine chemical industry, essence and flavor.
Background
The strawberry acid is also called 2-methyl-2-pentenoic acid, naturally exists in strawberries, is mostly trans-form, is edible spice which is allowed to be used in the regulation of the national standard GB 2760-1996, not only has the fragrance of fresh strawberries, but also has sweet berry-like fragrance and sour taste, and has mellow and durable flavor. The method is mainly used for preparing edible strawberries, hawthorns, cheeses, raspberries, tropical fruits and other essences; it can also be used for preparing food flavoring with citrus fragrance, and can be directly used for beverage and food processing. Besides being applied to edible essence, the strawberry acid is also applied to a daily chemical essence formula.
Currently, there are mainly 6 synthesis methods for 2-methyl-2-pentenoic acid:
1. 2-pentanone is used as an initial raw material, nucleophilic addition is carried out on the 2-pentanone and sodium cyanide, and the strawberry acid is synthesized through 4 steps of reactions such as cyano hydrolysis, cis-trans isomerization and the like. The method uses highly toxic cyanide, which is extremely harmful to the environment and life; and the 2-methyl-2-hydroxypentane carboxylic anhydride is (Z) -2-methyl-2-pentenoic acid, and the thermal isomerization conversion rate is not ideal.
2. The strawberry acid is synthesized by using 2-methyl pentanoic acid as a starting raw material through 5 steps of reactions such as alpha-bromination, esterification, hydrolytic dehydration, saponification and acidification.
3. The trans-2-methyl-2-pentenoic acid is obtained by using alpha-diethyl phosphono ethyl propionate as a starting material and carrying out 2-step treatment such as reaction with NaH, saponification, acidification and the like. The raw materials of the method are scarce, NaH is used, and no industrial production report is found.
4. Propionaldehyde and butanone are condensed under the catalysis of sulfuric acid to prepare 3-methyl-3-hexene-2-ketone; then obtaining the strawberry acid through haloform reaction, and the yield of the method is not high.
5. Taking 2-bromoethyl propionate as a raw material, firstly reacting with Zn, reacting with propionaldehyde in an ether solvent under an acidic condition to generate 3-hydroxy-2-methyl ethyl valerate, then heating, and dehydrating to generate 2-methyl-2-allyl ethyl acetate; then 2-methyl-2-pentenoic acid is generated through hydrolysis and acidification.
6. Propionaldehyde is subjected to aldol condensation reaction to obtain 2-methyl-2-pentenal, olefine aldehyde is selectively oxidized to generate corresponding 2-methyl-2-pentenoic acid, and finally, strawberry acid can be conveniently obtained through separation. The method has the advantages of cheap and easily obtained raw materials and mild reaction conditions, and is suitable for large-scale industrial production.
In addition, the 2-methyl-2-pentenal can also be used for synthesizing the strawberry acid through three (3) steps of reactions such as oximation, dehydration to form nitrile, hydrolysis and the like, and the method has the advantages of multiple reaction steps, complex byproducts, high product separation difficulty and unsuitability for industrial production.
Among the above synthetic methods of strawberry acid, the process 6 is a mainstream industrial production method of the current preparation of strawberry acid, that is: firstly, propionaldehyde is taken as a starting raw material, and an aldol condensation reaction is carried out under the action of an alkali catalyst to generate trans-2-methyl-2-pentenal; and then trans-2-methyl-2-pentenal is subjected to oxidation reaction under the action of an oxidant to prepare trans-2-methyl-2-pentenoic acid, namely trans-strawberry acid. The key points of the process are mainly the oxidation reaction steps, and according to literature reports, the most widely applied oxidation processes mainly comprise a silver nitrate/silver oxide process, a sodium chlorite process and a catalytic oxidation process.
In 1988, the first phase of essence and perfume cosmetics and U.S. Pat. No. 3,3162682 respectively report the reaction of silver nitrate and silver oxide as oxidants. Although the process is mature, the used oxidant is expensive, difficult to supply, high in process production cost and large in three wastes, and does not meet the requirements of modern production.
The sodium chlorite process is the main method for producing strawberry acid in the current market, and Chinese patents CN1270951A, CN1089085C, CN102653510A, CN104402701B and CN104892402A all report the reaction for preparing trans-strawberry acid by using sodium chlorite as an oxidant and obtain satisfactory results. But the process has the same obvious defects that at least one equivalent of oxidant is consumed, a large amount of waste salt, chlorine-containing wastewater and the like are generated in the production process, and the pressure of safety and environmental protection is higher.
The catalytic oxidation process uses oxygen or air as oxidant, and the process generally uses metal salts of cobalt, manganese and nickel as catalyst. However, the process has complex equipment, difficult process control, easy deep oxidation and low reaction yield.
The Reppe synthesis method is that olefin or alkyne, carbon monoxide and a nucleophilic reagent such as H are mixed2O、 ROH、RNH2And the like in the presence of a homogeneous catalyst to form carbonyl acids and derivatives thereof. The reaction has good atom economy and environmental friendliness, and accords with the development trend of green chemistry.
The invention aims to prepare the trans-strawberry acid by adopting a Reppe synthesis method to overcome the defects of the existing strawberry acid preparation process, namely, piperylene, carbon monoxide and water are used as raw materials to firstly carry out Reppe reaction to prepare a carbonyl acid compound, and then the trans-strawberry acid is obtained through isomerization of double bonds. In the prior art, reactions involving the preparation of carbonyl acid compounds starting from conjugated diolefins with carbon monoxide and water are relatively rare, mainly several patents of international shell, such as CN101137610, CN101142162, US4927892, etc. In these patents, palladium salts are used as catalysts for the reaction, but a mixture of 2-, 3-and 4-pentenoic acids is mainly obtained, with poor selectivity. The catalyst plays a decisive role in the selectivity and yield of the Reppe reaction, and the adoption of a proper catalyst to obtain the strawberry acid with high selectivity and yield is a technical problem to be solved at present.
Disclosure of Invention
In order to solve the problems in the prior art, the strawberry acid is prepared by a Reppe synthesis method, piperylene, carbon monoxide and water are used as raw materials, noble metal rhodium salt and organic phosphine ligand are used as catalysts, cis-trans isomeric intermediates of 2-methyl-3-pentenoic acid are obtained, and then trans-2-methyl-2-pentenoic acid, namely trans-strawberry acid, is generated by the isomerization reaction of the obtained intermediate products.
Specifically, the technical scheme is as follows:
the invention provides a method for synthesizing trans-2-methyl-2-pentenoic acid, which comprises the following steps:
the synthesis method of the invention preferably comprises the following steps:
(1) reacting piperylene, carbon monoxide and water under the action of a catalyst 1, and separating cis-trans isomers of 2-methyl-3-pentenoic acid from the obtained reaction liquid;
(2) the cis-trans isomer of the 2-methyl-3-pentenoic acid is subjected to isomerization reaction under the action of an acid catalyst 2, and trans-2-methyl-2-pentenoic acid, namely trans-strawberry acid, can be separated from the obtained reaction liquid.
Wherein, the catalyst of the reaction in the step (1) plays an important role in the conversion rate and selectivity of the product. In the Reppe reaction, salts and complexes of many transition metals such as Ni, Co, Fe, Rh, Ru, Pd, etc. can be used as catalysts, but different catalysts have quite different effects for a particular reaction. Therefore, it is technically difficult to develop a suitable catalyst for the reaction of preparing strawberry acid by the Reppe synthesis method.
The inventor of the application develops and obtains the catalyst with high selectivity and yield through technical research and development for many years, and research related to the application is funded by 'innovated talent support plan after doctor of Shandong province'.
Specifically, catalyst 1 comprises a noble metal catalyst and an organophosphine ligand. The noble metal catalyst and the organic phosphine ligand can better catalyze the reaction and obtain higher yield.
The noble metal catalyst is one of rhodium salts, and the rhodium catalyst has excellent catalytic activity in the reaction, high reaction conversion rate and good selectivity. The rhodium salt may be Rh (CO)2(acac)、 Rh2(CO)4Cl2、RhCl3·3H2O、Rh(NO3)3Is preferably Rh2(CO)4Cl2. The molar ratio of rhodium salt to piperylene is preferably (0.02-0.04): 1.
The organic phosphine ligand is one of spiro phosphorus Ligands, can be a monodentate ligand or a bidentate ligand, and is preferably one of the following spiro phosphorus Ligands (Ligands 1-4).
Further preferred are bidentate ligands Ligand 2 and Ligand4, which have greater steric hindrance and better selectivity than when monodentate ligands are used.
Compared with other types of ligands, the monodentate or bidentate spiro phosphorus ligand has a larger cone angle or bite angle of a complex formed by coordination with a metal, and a skeleton of the formed spiro complex has higher rigidity, so that the reaction has higher selectivity.
The molar ratio of the organophosphorus ligand to the noble metal rhodium salt in the step (1) is preferably (1.0-1.3): 1.
The reaction in step (1) may use a solvent, which is one of polar aprotic solvents miscible with water, and may be N, N-Dimethylformamide (DMF), 1, 3-dimethyl-2-imidazolidinone (DMI), dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), hexamethylphosphoric triamide (HMPA), preferably DMI and HMPA.
The molar ratio of raw material piperylene and water in the step (1) can be 1 (1-1.5), and the preferable range is 1 (1.1-1.2).
The reaction temperature of the step (1) is 90-140 ℃, preferably 100-130 ℃.
The pressure of the carbon monoxide in the step (1) is 2.0 to 3.5MPa, preferably 2.0 to 3.0 MPa.
Further, the separation mode in the step (1) is vacuum rectification. Cis-trans isomers of the intermediate 2-methyl-3-pentenoic acid and the solvent can be separated by adjusting the reflux ratio.
The solvent can be used for the next batch, and the catalyst and a small amount of leftover materials are used at the bottom of the kettle and can be directly used for the next batch.
The isomerization catalyst 2 in the step (2) is an acid catalyst.
The acid catalyst is an acetic acid solution of zinc chloride, and the mass concentration of the zinc chloride is 35-60%, preferably 40-50%.
When zinc chloride/acetic acid solution is used as a catalyst, the product almost quantitatively generates a trans-configuration, and when pure zinc chloride is used as the catalyst, 20-30% of cis-2-methyl-2-pentenoic acid is generated, so that the problem that the purification of the trans-2-methyl-2-pentenoic acid product is more difficult due to the existence of cis-isomers is caused.
During the reaction, zinc chloride increases the acidity of the 2-position C-H bond by activating the carbonyl group to make the C-H bond more susceptible to cleavage, while acetic acid forms a carbenium intermediate by activating the double bond. Whether the cis isomer or the trans isomer of the 2-methyl-3-pentenoic acid is formed into the same carbenium ion intermediate under the catalytic system, and then the dication intermediate is rearranged to generate the trans isomer-based strawberry acid. While the reaction process when only zinc chloride is used is probably not a process of a carbenium ion intermediate, so that the cis-trans isomer selectivity is not good during rearrangement.
The feeding amount of the zinc chloride/acetic acid solution is 5-15%, preferably 8-13% of the total mass of the cis-trans isomers of the 2-methyl-3-pentenoic acid.
The reaction temperature in the step (2) is 50-80 ℃, and preferably 60-70 ℃.
Furthermore, the separation method in the step (2) can adopt a washing and layering rectification mode. The specific steps can be that firstly, distilled water is used for washing reaction liquid after reaction for two times, upper oil phase is obtained through liquid separation, and then trans-2-methyl-2-pentenoic acid can be obtained through decompression and rectification of the upper oil phase.
For the purpose of facilitating an understanding of the synthetic routes of the present invention, the following is a list of principal reaction routes in one embodiment, which is merely exemplary and not limiting:
compared with the prior art, the invention has the following beneficial effects:
the invention develops a proper catalyst, prepares the trans-2-methyl-2-pentenoic acid by Reppe reaction, avoids the problems of long steps, low yield, high production cost and more three wastes of the existing route, can obtain a target product with high yield, environmental friendliness and high atom economy, further provides a new route selection for synthesizing the trans-2-methyl-2-pentenoic acid, and has the following advantages:
1. the reaction yield is higher, the atom utilization rate is good, and the two-step reaction yield can respectively reach more than 82 percent and 94 percent.
2. The three wastes are less in the reaction process, and the method is environment-friendly. The raw materials are completely utilized, and no waste gas is generated.
3. The reaction adopts cheap pentadiene, carbon monoxide and water as raw materials, and the adopted noble metal catalyst can be recycled, so that the method has the advantages of simple operation process, low requirements on instruments and equipment and lower production cost.
4. The synthesis method disclosed by the invention can reduce reaction impurities, is clean and environment-friendly, has higher economic and environment-friendly benefits, is beneficial to the production of strawberry acid, and provides reference for other acidic compounds with similar structures.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
The product contents in the following examples are the isolated yields unless otherwise specified.
Examples 1 to 25
Adding catalyst 1 (rhodium salt and ligand) into a high-pressure reaction kettle, adding a solvent, stirring to ensure that the rhodium salt and the ligand are coordinated and dissolved, and then adding piperylene and water. And closing the reaction kettle, replacing the air in the kettle with nitrogen for three times, replacing the air with carbon monoxide for three times, heating to the set temperature, and supplementing pressure to the set pressure with the carbon monoxide. Starting reaction, detecting the reaction end point by gas phase, and then transferring the reaction liquid to a rectifying tower for decompression, rectification and separation to obtain cis-trans isomers of the 2-methyl-3-pentenoic acid. The results of the specific experiments are shown in Table 1 below.
TABLE 1 Experimental results of step (1)
From the results in the table above, we can conclude that: comparative examples 1 to 4, the rhodium salt is preferably Rh2(CO)4Cl2(ii) a Comparative examples 2,8-12, more sterically hindered bidentate ligands are preferred, the molar ratio of ligand to rhodium salt preferably being (1.0-1.3):1, and the molar ratio of rhodium salt to piperylene preferably being (0.02-0.04): 1; comparative examples 12 to 21 show that the amount of water used is preferably (1.1 to 1.2):1 (molar ratio of water to piperylene), the pressure of carbon monoxide is preferably 2.0 to 3.0MPa, and the reaction temperature is preferably 100-; finally, DMI and HMPA were found to be preferred by solvent screening.
Examples 26 to 36
Adding a certain amount of catalyst 2 (zinc chloride/acetic acid solution) into the 2-methyl-3-pentenoic acid cis-trans isomer obtained in the step (1), and heating to a set temperature for carrying out isomerization reaction. And detecting the reaction end point by using a gas phase, washing the reaction twice by using distilled water after the reaction is finished, separating the liquid to obtain an upper oil phase, and then transferring the reaction liquid to a rectifying tower for decompression, rectification and separation to obtain the trans-strawberry acid. The results of the specific experiments are shown in Table 2 below.
TABLE 2 Experimental results of step (2)
From the results in the table above, we can conclude that: the feeding amount of the zinc chloride/acetic acid catalyst is preferably 8-13% (mass ratio to cis-trans isomer), the mass concentration of the zinc chloride in the zinc chloride/acetic acid solution is preferably 40-50%, and the reaction temperature is preferably 60-70 ℃.
Comparative examples 1 to 7
Comparative examples 1 to 7 are comparisons made on the basis of example 25, in which the rhodium salt of the noble metal catalyst of example 25 was changed to another metal catalyst such as palladium acetate, or the ligand was changed to another phosphorus ligand such as triphenylphosphine. The experimental results are shown in table 3 below.
TABLE 3 comparative experimental results
As can be seen from the above comparative results, when palladium, ruthenium, cobalt, iron were used as the catalyst, the selectivity of the reaction was poor (comparative examples 1 to 4), while the yield was also significantly reduced when the spiro ligand was changed to another phosphorus ligand (comparative examples 5 to 7).
Comparative example 8
Comparative example 8 a comparison was made on the basis of example 34, changing the zinc chloride/acetic acid catalyst of example 34 to a pure zinc chloride catalyst, without the addition of acetic acid to the reaction. The results of the experiment are shown in table 4 below.
Table 4 comparative experimental results
From the experimental results, it is known that the catalyst adopts pure zinc chloride instead of zinc chloride/acetic acid solution as the catalyst, and although the reaction also has higher conversion rate, the selectivity of the trans-strawberry acid is lower. In the resulting strawberry acid mixture, trans-strawberry acid was about 70% and cis-strawberry acid was about 25%.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. A method for synthesizing trans-2-methyl-2-pentenoic acid is characterized by comprising the following steps: (1) carrying out catalysis on piperylene, carbon monoxide and water serving as raw materials under the action of a catalyst 1 and a solvent at a certain reaction temperature and pressure to obtain a cis-trans isomer of 2-methyl-3-pentenoic acid; (2) under the action of a catalyst 2, carrying out isomerization reaction on cis-isomer of 2-methyl-3-pentenoic acid to obtain trans-2-methyl-2-pentenoic acid;
the catalyst 1 is rhodium salt and organic phosphine ligand, and the rhodium salt is Rh (CO)2(acac)、Rh2(CO)4Cl2、RhCl3·3H2O、Rh(NO3)3One or more of;
the organic phosphine ligand is one of the following spiro phosphorus Ligands (Ligands 1-4)
The catalyst 2 is a zinc chloride/acetic acid solution.
2. The synthesis method of claim 1, wherein the molar ratio of the organophosphine ligand to the rhodium salt is (1.0-1.3): 1.
3. The synthesis process of claim 1, wherein the molar ratio of rhodium salt to piperylene is (0.02-0.04): 1.
4. The synthesis method according to claim 1, wherein the mole ratio of piperylene to water is 1 (1-1.5).
5. The synthesis process according to claim 1, wherein the pressure of carbon monoxide is 2.0-3.5 Mpa.
6. The synthesis method according to claim 1, wherein the reaction temperature of the step (1) is 90-140 ℃.
7. The method of synthesis of claim 1, wherein the solvent is one of DMI or HMPA.
8. The synthesis method according to claim 1, characterized in that in the catalyst 2, the mass concentration of zinc chloride is 40-50%, and the dosage of zinc chloride/acetic acid solution is 8-13% of the total mass of 2-methyl-3-pentenoic acid cis-trans isomers.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| US4000327A (en) * | 1974-07-22 | 1976-12-28 | International Flavors & Fragrances Inc. | Flavoring with cis esters of 2-methyl-3-pentenoic acid |
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