CN108002967B - Preparation method of tiglic aldehyde derivative - Google Patents
Preparation method of tiglic aldehyde derivative Download PDFInfo
- Publication number
- CN108002967B CN108002967B CN201711215887.6A CN201711215887A CN108002967B CN 108002967 B CN108002967 B CN 108002967B CN 201711215887 A CN201711215887 A CN 201711215887A CN 108002967 B CN108002967 B CN 108002967B
- Authority
- CN
- China
- Prior art keywords
- derivative
- reaction
- aldehyde
- group
- isoamylene
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/06—Formation or introduction of functional groups containing oxygen of carbonyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a preparation method of tiglic aldehyde derivatives, which comprises the following steps: an isomer of the following formula (I)The pentene derivative is subjected to catalytic oxidation in the presence of a catalyst to generate tiglic aldehyde derivatives shown as the following formula (II), wherein the catalyst is a non-metal oxide:
wherein R in the formula (I) or the formula (II) is selected from aliphatic hydrocarbon group, aryl group, aralkyl group, halogen, ester group, acyloxy group, amido group or alkoxy group. The preparation method of the tiglic aldehyde derivative provided by the invention has the characteristics of few reaction steps, simple process, cheap and easily available raw materials and the like.
Description
Technical Field
The invention relates to the technical field of preparation of tiglic aldehyde derivatives, and particularly relates to a preparation method of tiglic aldehyde derivatives.
Background
Tiglic aldehyde derivatives, also known as cisolic aldehyde derivatives. In the food industry, the tiglic aldehyde derivative can be used for preparing edible essences such as vanilla, tropical fruits, almond, cherry and the like; in the chemical synthesis industry, tiglic aldehyde derivatives are important intermediates for preparing various apocarotenal and diapocarcinol and vitamin A. The tiglic aldehyde derivative can also be used for synthesizing other organic matters.
The tiglic aldehyde derivative has the following structural formula:
At present, there are various methods for synthesizing tiglic aldehyde derivatives. Among them, a well-known method is to prepare tiglic aldehyde derivatives from propionaldehyde and acetaldehyde derivatives by intermolecular condensation. However, in the case of cross condensation of these two different aldehyde compounds, the respective aldehyde compounds may undergo condensation reaction itself using a known aldehyde condensation catalyst such as sodium hydroxide, etc., thereby causing a decrease in the selectivity of producing tiglic aldehyde derivatives for the purpose of cross condensation; at the same time, this also brings about inevitable troubles in the purification operation.
Chinese patent applications CN1495151A and CN1178783A both disclose a method for preparing acetoxytiglic aldehyde from acetal and allyl ether as raw materials through enol ether condensation, cracking, halogenation and acetoxylation. However, the method has the defects of more reaction steps, low product yield (about 53%), more reaction waste residues and liquid waste, and the like, and is poor in environmental protection and economical efficiency.
U.S. Pat. No. 5,059,325 describes a process for preparing 2-ethyl-2-hexenal by aldol condensation using MgO-Al2O3As a catalyst, the condensation reaction of valeraldehyde was carried out in a fixed bed at a reaction temperature of 150 ℃. The product yield is not good due to the high reaction temperature.
Therefore, in order to solve the above-mentioned deficiencies, a new process for preparing a tiglic aldehyde derivative is needed to be found in the prior art, which has the problems of tedious process, low yield, and difficult post-treatment.
Disclosure of Invention
The invention provides a method for preparing tiglic aldehyde derivatives, which overcomes the defects in the prior art and has the characteristics of few reaction steps, simple process, cheap and easily obtained raw materials and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of tiglic aldehyde derivatives, which comprises the following steps: the method comprises the following step of carrying out oxidation reaction on an isoamylene derivative shown as a formula (I) in the presence of a catalyst to generate tiglic aldehyde derivative shown as a formula (II), wherein the catalyst is a non-metal oxide:
wherein R in the formula (I) or the formula (II) is selected from one of aliphatic hydrocarbon group, aryl group, aralkyl group, halogen, ester group, acyloxy group, acylamino group or alkoxy group;
preferably, R in formula (I) or formula (II) is any one selected from aralkyl group having 6 to 9 carbon atoms, chlorine, bromine, acyloxy group having 1 to 4 carbon atoms, carboxamide group, methoxy group and ethoxy group.
The invention adopts the nonmetallic oxide to catalyze the isoamylene derivative to carry out oxidation reaction to prepare the tiglic aldehyde derivative, has simple process, less reaction steps, better reaction selectivity and product yield, and cheap and easily obtained raw material isoamylene derivative, and can reduce the production cost.
In the preparation method, in order to obtain better catalytic effect and achieve the purposes of improving reaction selectivity and product yield, the nonmetal oxide is preferably any one or at least two nonmetal oxides in IIIA-VIIA groups in the periodic table of elements; further preferably one or at least two oxides of Si, P, S, Se, Te and I; more preferably Se and/or Te.
In the preparation method of the present invention, in order to obtain better reaction selectivity and product yield, the non-metallic oxide is more preferably an acidic non-metallic oxide, more preferably one or at least two of phosphorus trioxide, phosphorus pentoxide, silicon dioxide, selenium dioxide and tellurium dioxide, and even more preferably one or two of selenium dioxide and tellurium dioxide.
In the preparation method of the present invention, the oxidation reaction is preferably performed in the presence of an aqueous isopropanol solution, and preferably, the mass ratio of the isoamylene derivative to the aqueous isopropanol solution is 1:10 to 1:50, preferably 1:15 to 1: 25.
In the preparation method, the aldehyde compound is preferably added in the reaction system, and the reaction selectivity and the product yield can be greatly improved through the synergistic effect with the catalyst. In order to better promote the oxidation reaction and obtain better reaction selectivity and product yield, it is further preferable that the aldehyde compound is one or at least two of aldehyde compounds having 1 to 10 carbon atoms, and more preferably one or at least two of saturated aliphatic aldehydes having 1 to 5 carbon atoms. The formaldehyde is further preferably selected to obtain a more remarkable effect of promoting the oxidation reaction, the formaldehyde has small volume and small corresponding chemical steric hindrance, is more favorable for free shuttle in the chemical reaction process, can better induce the formation of the intermediate transition state, quickens the electron transfer of the transition state, shortens the reaction time and improves the product yield. The reaction process of the present invention is shown below by taking formaldehyde as the aldehyde compound and selenium dioxide as the catalyst, and it should be noted that the following description is only an example and is not a limitation of the present invention:
in the preparation method of the present invention, the addition amount of the aldehyde compound is preferably more than 0 and 1000ppm or less relative to the total mass of the isoamylene derivative and the aqueous isopropanol solution. The inventor finds that the addition amount is less than or equal to 1000ppm, the reaction rate can be improved, and the product yield can be increased; when the addition amount is larger than the above addition amount, although the reaction rate can be greatly increased, the side reaction is remarkably increased, resulting in a decrease in the product yield. In a more preferable scheme, the addition amount of the aldehyde compound is 100-900ppm, and the reaction rate and the product yield are both higher by adopting the preferable addition amount of the aldehyde compound; in a more preferred embodiment, the aldehyde compound is more preferably 500-700 ppm.
In the preparation method of the invention, the dosage of the catalyst is preferably 0.1-10 wt%, more preferably 0.5-2.5 wt% of the total mass of the isoamylene derivative and the isopropanol aqueous solution, and the preferred dosage of the catalyst is adopted, so that not only can a higher reaction conversion rate be obtained, but also the waste of the catalyst is not caused; the use amount of the catalyst is too small, which is not beneficial to obtaining higher conversion rate; however, the catalyst is used in an excessive amount, so that the reaction conversion rate is not increased correspondingly, waste is caused, and the cost is increased.
In the preparation method of the present invention, when the aldehyde compound and the aqueous isopropanol solution are added to the reaction system at the same time, a preferred embodiment is to first feed the isoamylene derivative and the aqueous isopropanol solution, and then add the catalyst and the aldehyde compound to the reaction system.
According to the preparation method, the oxidation reaction can be carried out under a relatively mild condition, and the temperature of the oxidation reaction is preferably 30-150 ℃, and more preferably 40-60 ℃; the absolute pressure of the oxidation reaction is preferably 0.01MPa to 2MPa, more preferably 0.1MPa to 0.4 MPa; the reaction time of the oxidation reaction is preferably 1 to 10 hours, more preferably 3 to 6 hours.
In a preferred embodiment, the preparation method of the present invention further comprises the following steps: after the reaction is finished, removing the catalyst in the reaction liquid, and rectifying and separating to obtain the tiglic aldehyde derivative. In one embodiment, the catalyst in the reaction solution may be removed by cooling the reaction solution and allowing the reaction solution to stand for layering. Preferably, the prepared tiglic aldehyde derivative is separated by adopting a vacuum rectification mode, the reflux ratio of the vacuum rectification separation is 1:1-8:1, preferably 2:1-5:1, the top pressure of a rectification tower is 50Pa-2000Pa, preferably 80Pa-200Pa, and the total plate number of the rectification tower is 30-100, preferably 50-80.
The preparation method is particularly suitable for preparing the tiglic aldehyde derivative by a one-pot production process.
The technical scheme provided by the invention has the following beneficial effects:
1. the preparation method has the advantages of simple and safe operation, high yield and the like, and the product yield can reach more than 70 percent and reaches 70 to 85 percent in some embodiments.
2. The method adopts oxidation reaction to prepare the tiglic aldehyde derivative, and is a new technical route for synthesizing the tiglic aldehyde derivative with less reaction steps and simple flow. The invention uses non-metal oxide to catalyze the oxidation reaction, especially adds aldehyde additive, to improve the reaction selectivity and product yield. Meanwhile, the raw material isoamylene derivative used by the invention is cheap and easy to obtain, and the production cost is effectively reduced.
3. The preparation method is particularly suitable for the one-pot method to carry out the oxidation reaction of the isoamylene derivative, simplifies the production flow, reduces the equipment and the operators, and can improve the production efficiency and save the equipment cost and the production cost.
4. The preparation method is economic and environment-friendly, has simple equipment, produces no waste slag and waste liquid in the reaction, and is an economic and environment-friendly green synthesis technical route.
Drawings
Fig. 1 to 7: the 1H-NMR spectra of the target products of examples 1 to 7 were obtained in this order.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples. Each of the raw materials described in the examples was purchased from commercial sources, mainly from the company Profenox and Merck. Wherein: 2-methyl-4-chloro-2-butene, 2-methyl-4-bromo-2-butene, 2-methyl-4-phenyl-2-butene, 2-methyl-4-formyloxy-2-butene were purchased from carbofuran reagent company, 2-methyl-4-acetoxy-2-butene, 2-methyl-4-carboxamido-2-butene, 2-methyl-4-ethoxy-2-butene were purchased from merck reagent company.
The Gas Chromatogram (GC) analysis conditions used in the following examples are illustrated below:
chromatography apparatus: agilent 7890A;
the type of the chromatographic column: DB-5, inner diameter 320.00 μm, length 30.0m, maximum temperature: 325.0 ℃;
temperature rising procedure: first 50 ℃ for 1 minute, then 20 ℃/min to 250 ℃ for 1 minute, total run time 12 minutes.
Example 1
Synthesis of chloro tiglic aldehyde:
in a 500mL reaction kettle, 2-Methyl-4-chloro-2-butene (10.66 g, 0.1mol), aqueous isopropanol solution (210 g), formaldehyde (0.11 g), and SeO22.1g, stirring uniformly, heating to 50 ℃, keeping the temperature and stirring for 5 hours under normal pressure, after the reaction is completed, cooling the reaction liquid to room temperature, standing and layering, and separating the oil phase in a rectifying tower with a reflux ratio of 2:1, an absolute pressure of 100Pa at the top of the tower and a total number of 80 plates to obtain 86.6g of chloro-tiglic aldehyde (the purity is 98 percent by GC analysis) and the reaction yield is 71.5 percent.
The 1H-NMR spectrum of the obtained product chloro tiglic aldehyde is shown in figure 1.
Example 2
Synthesis of bromotiglic aldehyde:
in a 500mL reaction vessel, 15.11g (0.1mol) of 2-methyl-4-bromo-2-butene, 210g of an aqueous isopropanol solution, 0.11g of formaldehyde and SeO were charged22.1g, stirring uniformly, heating to 55 ℃, keeping the temperature and stirring for 4 hours under normal pressure, after the reaction is completed, cooling the reaction liquid to room temperature, standing and layering, and separating the oil phase in a rectifying tower with a reflux ratio of 2:1, an absolute pressure of 100Pa at the top of the tower and a total number of 80 plates to obtain 130.3g of bromotiglic aldehyde (the purity is 98 percent by GC analysis) and the reaction yield is 78.3 percent.
The 1H-NMR spectrum of the obtained product, namely bromotiglic aldehyde, is shown in a figure 2. :
example 3
Synthesis of gamma-phenyl tiglic aldehyde:
into a 500mL reaction vessel, 14.82g (0.1mol) of 2-methyl-4-phenyl-2-butene, 210g of an aqueous isopropanol solution, 0.11g of formaldehyde and SeO were charged22.1g, stirring uniformly, heating to 60 ℃, keeping the temperature and stirring for 4 hours under normal pressure, after the reaction is completed, cooling the reaction liquid to room temperature, standing and layering, and separating the oil phase in a rectifying tower with the reflux ratio of 2:1, the pressure at the top of the tower of 100Pa and the total number of plates of 80 to obtain 115.6g of gamma-phenyl tiglic aldehyde (the purity is 98.8 percent by GC analysis), wherein the reaction yield is 71.3 percent.
The 1H-NMR spectrum of the obtained product gamma-phenyl tiglic aldehyde is shown in figure 3.
Example 4
Synthesis of gamma-formyloxy tiglic aldehyde:
in a 500mL reaction kettle11.6g (0.1mol) of 2-methyl-4-formyloxy-2-butene, 210g of an aqueous isopropanol solution, 0.11g of formaldehyde and SeO were introduced22.1g, stirring uniformly, heating to 50 ℃, keeping the temperature and stirring for 4 hours under normal pressure, after the reaction is completed, cooling the reaction liquid to room temperature, standing and layering, and separating the oil phase in a rectifying tower with the reflux ratio of 2:1, the pressure at the top of the tower of 100Pa and the total number of plates of 80 to obtain 94.5g of gamma-formyloxy tiglic aldehyde (the GC analysis purity is 98.5 percent) and the reaction yield is 72.7 percent.
The 1H-NMR spectrum of the obtained product gamma-formyloxy tiglic aldehyde is shown in figure 4.
Example 5
Synthesis of gamma-acetoxyl tiglic aldehyde:
into a 500mL reaction vessel, 13g (0.1mol) of 2-methyl-4-acetoxy-2-butene, 210g of an aqueous isopropanol solution, 0.11g of formaldehyde and SeO were charged22.1g, stirring uniformly, heating to 50 ℃, keeping the temperature and stirring for 5 hours under normal pressure, after the reaction is completed, cooling the reaction liquid to room temperature, standing and layering, and separating the oil phase in a rectifying tower with a reflux ratio of 2:1, an absolute pressure of 100Pa at the top of the tower and a total number of 80 plates to obtain 103.9g of gamma-acetoxytiglic aldehyde (with a GC purity of 98.6%) and a reaction yield of 72.14%.
The 1H-NMR spectrum of the obtained product gamma-acetoxytiglic aldehyde is shown in FIG. 5.
Example 6
Synthesizing gamma-formamido tiglic aldehyde:
in a 500mL reaction vessel, 11.5g (0.1mol) of 2-methyl-4-carboxamido-2-butene, 210g of an aqueous isopropanol solution, 0.11g of formaldehyde and SeO were charged22.1g, stirring uniformly, heating to 55 ℃, keeping the temperature and stirring for 4 hours under normal pressure, after the reaction is completed, cooling the reaction liquid to room temperature, standing and layering, and separating the oil phase in a rectifying tower with the reflux ratio of 2:1, the pressure at the top of the tower of 100Pa and the total number of plates of 80 to obtain 94.5g (the GC purity is 98.4%) of gamma-formamido tiglic aldehyde, wherein the reaction yield is 73.2%.
The 1H-NMR spectrum of the obtained product gamma-formamido tiglic aldehyde is shown in figure 6.
Example 7
Synthesis of gamma-ethoxy tiglic aldehyde:
into a 500mL reaction vessel, 11.6g (0.1mol) of 2-methyl-4-ethoxy-2-butene, 210g of an aqueous isopropanol solution, 0.11g of formaldehyde and SeO were charged22.1g, stirring uniformly, heating to 50 ℃, keeping the temperature and stirring for 5 hours under normal pressure, after the reaction is completed, cooling the reaction liquid to room temperature, standing and layering, and separating the oil phase in a rectifying tower with the reflux ratio of 2:1, the pressure at the top of the tower of 100Pa and the total number of plates of 80 to obtain 110.5g (the GC purity is 98.2%) of the gamma-ethoxytiglic aldehyde, wherein the reaction yield is 84.8%.
The 1H-NMR spectrum of the obtained product gamma-ethoxytiglic aldehyde is shown in FIG. 7.
Example 8
Synthesis of gamma-ethoxy tiglic aldehyde:
in a 500mL reaction vessel, 11.6g (0.1mol) of 2-methyl-4-ethoxy-2-butene, 210g of an aqueous isopropanol solution, 0.28g of formaldehyde and SeO were charged22.1g, stirring uniformly, heating to 50 ℃, keeping the temperature and stirring for 5 hours under normal pressure, after the reaction is completed, cooling the reaction liquid to room temperature, standing and layering, and separating the oil phase in a rectifying tower with a reflux ratio of 2:1, an absolute pressure of 100Pa at the top of the tower and a total number of 80 plates to obtain 107.0g (with a GC purity of 98.1%) of gamma-ethoxytiglic aldehyde, wherein the reaction yield is 82.1%.
The amount of formaldehyde used was increased compared to example 8 and example 7 (at > 1000ppm based on the sum of the masses of isoamylene derivative and aqueous isopropanol), although better yields were obtained, but it was reduced compared to example 7.
1H-NMR spectrum of product: see example 7 for a spectrum.
Example 9
Synthesis of gamma-ethoxy tiglic aldehyde:
in a 500mL reaction vessel, 11.6g (0.1mol) of 2-methyl-4-ethoxy-2-butene, 210g of an aqueous isopropanol solution and SeO were charged22.1g, stirring uniformly, heating to 50 ℃, keeping the temperature and stirring for 12 hours under normal pressure, after the reaction is completed, cooling the reaction liquid to room temperature, standing and layering, and separating the oil phase in a rectifying tower with the reflux ratio of 2:1, the pressure at the top of the tower of 100Pa and the total number of plates of 80 to obtain 95.7g (GC purity) of the gamma-ethoxytiglic aldehyde98.2%), reaction yield 73.5%.
In example 9, the reaction yield was greatly reduced compared to example 7 without the addition of formaldehyde.
Example 10
Synthesis of gamma-ethoxy tiglic aldehyde:
into a 500mL reaction vessel, 11.6g (0.1mol) of 2-methyl-4-ethoxy-2-butene, 210g of an aqueous isopropanol solution, 0.16g of acetaldehyde, and SeO were charged22.1g, stirring uniformly, heating to 50 ℃, keeping the temperature and stirring for 5 hours under normal pressure, after the reaction is completed, cooling the reaction liquid to room temperature, standing and layering, and separating the oil phase in a rectifying tower with the reflux ratio of 2:1, the pressure at the top of the tower of 100Pa and the total number of plates of 80 to obtain 104.9g of gamma-ethoxytiglic aldehyde (the GC purity is 98.2%) and the reaction yield is 80.5%.
This example also gave better reaction yields when acetaldehyde was used instead of formaldehyde than in example 7, but was reduced compared to example 7 when formaldehyde was used
Example 11
Synthesis of gamma-ethoxy tiglic aldehyde:
in a 500mL reaction vessel, 11.6g (0.1mol) of 2-methyl-4-ethoxy-2-butene, 210g of an aqueous isopropanol solution, 0.11g of formaldehyde and SiO were charged21.14g, stirring uniformly, heating to 50 ℃, keeping the temperature and stirring for 5 hours under normal pressure, after the reaction is completed, cooling the reaction liquid to room temperature, standing and layering, and separating an oil phase in a rectifying tower with a reflux ratio of 2:1, an absolute pressure of 100Pa at the top of the tower and a total number of 80 plates to obtain 102.4g (with a GC purity of 98.3%) of gamma-ethoxytiglic aldehyde, wherein the reaction yield is 78.6%.
In this example, SiO was used as compared with example 72Replacement of SeO2It also gives better yields, but is slightly inferior to the use of SeO2Example 7 of (4).
It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (13)
1. A preparation method of tiglic aldehyde derivatives is characterized by comprising the following steps: the method comprises the following step of carrying out oxidation reaction on an isoamylene derivative shown as a formula (I) in the presence of a catalyst, an aldehyde compound and an isopropanol aqueous solution to generate tiglic aldehyde derivative shown as a formula (II) in the specification, wherein the catalyst is a non-metal oxide:
wherein R in formula (I) or formula (II) is selected from aliphatic alkyl, aryl, aralkyl, halogen, ester group, acyloxy, amido or alkoxy;
the non-metallic oxide is one or two of silicon dioxide and selenium dioxide;
the aldehyde compound is one or at least two of saturated aliphatic aldehydes with 1-5 carbon atoms.
2. The method according to claim 1, wherein R in formula (I) or formula (II) is selected from any one of aralkyl group having 6 to 9 carbon atoms, chlorine, bromine, acyloxy group having 1 to 4 carbon atoms, carboxamide group, methoxy group, or ethoxy group.
3. The method according to claim 1 or 2, wherein the mass ratio of the isoamylene derivative to the aqueous isopropanol solution is from 1:10 to 1: 50.
4. The method according to claim 3, wherein the mass ratio of the isoamylene derivative to the aqueous solution of isopropyl alcohol is 1:15 to 1: 25.
5. The process according to claim 1, wherein the aldehyde compound is formaldehyde.
6. The process according to claim 1 or 2, wherein the aldehyde compound is added in an amount of more than 0ppm and 1000ppm or less relative to the total mass of the isoamylene derivative and the aqueous isopropanol solution.
7. The process according to claim 6, wherein the aldehyde compound is added in an amount of 100-900ppm based on the total mass of the isoamylene derivative and the aqueous solution of isopropyl alcohol.
8. The process according to claim 1 or 2, wherein the catalyst is used in an amount of 0.1 to 10% by weight based on the total mass of the isoamylene derivative and the aqueous solution of isopropyl alcohol.
9. The process according to claim 1 or 2, wherein the catalyst is used in an amount of 0.5 to 2.5% by weight based on the total mass of the isoamylene derivative and the aqueous solution of isopropyl alcohol.
10. The production method according to any one of claims 1 to 2, wherein the temperature of the oxidation reaction is 30 ℃ to 150 ℃;
the absolute pressure of the oxidation reaction is 0.01MPa-2 MPa;
the reaction time of the oxidation reaction is 1 to 10 hours.
11. The process according to any of claims 1-2, wherein the catalyst is removed from the reaction mixture after the reaction is completed, and the produced tiglic aldehyde derivative is separated by distillation.
12. The preparation method according to claim 11, wherein the prepared tiglic aldehyde derivative is separated by vacuum distillation, the reflux ratio of the vacuum distillation separation is 1:1-8:1, the top pressure of the distillation column is 50-2000 Pa, and the total number of plates of the distillation column is 30-100.
13. The production method according to any one of claims 1 to 2, wherein the tiglic aldehyde derivative is produced by a one-pot method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711215887.6A CN108002967B (en) | 2017-11-28 | 2017-11-28 | Preparation method of tiglic aldehyde derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711215887.6A CN108002967B (en) | 2017-11-28 | 2017-11-28 | Preparation method of tiglic aldehyde derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108002967A CN108002967A (en) | 2018-05-08 |
| CN108002967B true CN108002967B (en) | 2021-01-29 |
Family
ID=62052470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711215887.6A Active CN108002967B (en) | 2017-11-28 | 2017-11-28 | Preparation method of tiglic aldehyde derivative |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108002967B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997112B (en) * | 2018-07-25 | 2021-07-23 | 万华化学集团股份有限公司 | Preparation method of 4-acetoxyl-2-methyl-2-butenal |
| CN111675613B (en) * | 2020-05-29 | 2023-01-13 | 万华化学集团股份有限公司 | Preparation method of 4-acetoxyl-2-methyl-2-butenal |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1735578A (en) * | 2003-01-06 | 2006-02-15 | 旭化成化学株式会社 | Process for producing alcohol and/or ketone |
| CN101088608A (en) * | 2007-06-13 | 2007-12-19 | 中国科学院过程工程研究所 | Prepn process of catalyst for selective oxidation of isobutene to produce methyl acraldehyde |
| CN101709026A (en) * | 2009-10-20 | 2010-05-19 | 浙江医药股份有限公司维生素厂 | Method for synthesizing 3-methyl-2-butene aldehyde |
-
2017
- 2017-11-28 CN CN201711215887.6A patent/CN108002967B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1735578A (en) * | 2003-01-06 | 2006-02-15 | 旭化成化学株式会社 | Process for producing alcohol and/or ketone |
| CN101088608A (en) * | 2007-06-13 | 2007-12-19 | 中国科学院过程工程研究所 | Prepn process of catalyst for selective oxidation of isobutene to produce methyl acraldehyde |
| CN101709026A (en) * | 2009-10-20 | 2010-05-19 | 浙江医药股份有限公司维生素厂 | Method for synthesizing 3-methyl-2-butene aldehyde |
Non-Patent Citations (6)
| Title |
|---|
| Application of benzyl protecting groups in the synthesis of prenylated aromatic compounds;Odejinmi, Sina I.等;《Tetrahedron Letters》;20050413;第46卷(第22期);第149-156页 * |
| Coumarins from the herb Cnidium monnieri and chemically modified derivatives as antifoulants against Balanus albicostatus and Bugula neritina larvae;Wang, Zhan-Chang等;《 International Journal of Molecular Sciences》;20130109;第14卷;第1197-1206页 * |
| Development of a synthesis of lankacidins:an investigation into 17-membered ring formation,;Mata,Ernesto G.等;《Journal of the Chemical Society》;19950101(第7期);第785-799页 * |
| Didehydrofarnesyl diphosphate: an intrinsically fluorescent inhibitor of protein farnesyltransferase;Liu, Xiao-hui等;《Bioorganic & Medicinal Chemistry Letters》;20061231;第14卷(第9期);第2137-2140页 * |
| Regio- and enantioselective functionalization of acyclic polyprenoids;Barrero, Alejandro F.等;《Journal of the Mexican Chemical Society》;20061231;第50卷(第4期);第3871-3874页 * |
| Synthesis of Aromatic Bisabolene Natural Products via Palladium-Catalyzed Cross-Couplings of Organozinc Reagents;Vyvyan, James R.等;《Journal of Organic Chemistry》;20040603;第69卷(第7期);第2461-2468页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108002967A (en) | 2018-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Clarke et al. | Dearomatisation approaches to spirocyclic dienones via the electrophilic activation of alkynes | |
| CN108002967B (en) | Preparation method of tiglic aldehyde derivative | |
| CN106977383B (en) | Method for preparing citral | |
| EP2546226B1 (en) | 1-methoxyl-2,6,10-trimethyl-1,3,5,9-undec-tetraene and preparation method and uses thereof | |
| JP2017508727A (en) | Method for producing arylpropene | |
| EP1999097B1 (en) | Curcumin synthesis | |
| CN102206142B (en) | Method for preparing 3-methoxyl-3-methyl-1-butanol | |
| US4072660A (en) | Process for the manufacture of resorcinols | |
| EP2048139A1 (en) | PROCESS FOR PRODUCTION OF (±)-3a,6,6,9a TETRAMETHYLDECAHYDRONAPHTHO[2,1-b]FURAN-2(1H)-ONE | |
| Castellucci et al. | Synthesis of sterculic acid | |
| US4097531A (en) | Substituted cyclopropane process and product | |
| US2387366A (en) | Pyrolysis of pyran derivatives | |
| CN111056924B (en) | Phenolic compound and preparation method and application thereof | |
| CN107344904B (en) | Method for generating methyl ketone by catalytic oxidation of olefin with palladium | |
| DK170370B1 (en) | Process for the preparation of 3- (alkylphenyl) propanal | |
| CN108997117B (en) | Novel method for preparing 4-acetoxyl-2-methyl-2-butenal | |
| Moussaoui et al. | Catalyzed Knoevenagel reactions on inorganic solid supports: Application to the synthesis of coumarine compounds | |
| DE2437983B2 (en) | Process for the production of resorcinols | |
| CN1564797A (en) | Method for producing 6-methylheptane-2-one and the use thereof | |
| US4009202A (en) | 2(or 3)-methyl-1-acetoxy-4-alkoxy (or phenoxy)-1,3-butadienes | |
| EP0077635B1 (en) | Substituted esters and alcohols | |
| CN104230879A (en) | Simple and convenient preparation method of 2-((4R,6S)-6-formyl-2,2-disubstituted-1,3-dioxane-4-yl)acetate | |
| Cui et al. | Iridium‐Catalyzed Allylic Alkylations of Sodium Phenyl Selenide | |
| US5627288A (en) | Method for producing rosefuran precursor and intermediates therefor | |
| EP3207019B1 (en) | Method for producing specific alpha, beta-unsaturated aldehydes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |