CN108047013B - Synthetic method of isopentenal - Google Patents
Synthetic method of isopentenal Download PDFInfo
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- CN108047013B CN108047013B CN201711355314.3A CN201711355314A CN108047013B CN 108047013 B CN108047013 B CN 108047013B CN 201711355314 A CN201711355314 A CN 201711355314A CN 108047013 B CN108047013 B CN 108047013B
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- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
- C07C45/66—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups by dehydration
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- 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
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/58—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in three-membered rings
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- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
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Abstract
The invention provides a synthesis method of isopentenal, which comprises the following steps: and (3) performing hydroformylation reaction on epoxy isobutane to obtain hydroxyisovaleraldehyde, and performing intramolecular dehydration reaction on the hydroxyisovaleraldehyde to obtain the isopentenal. The invention provides a synthesis method of the isopropenal without rigorous reaction conditions.
Description
Technical Field
The invention relates to the technical field of preparation of isopentenal, and particularly relates to a synthesis method of isopentenal.
Background
Isopentenal (3-methyl-2-en-1 butanal) is a key intermediate in the production of vitamin E, vitamin A and citral, a fragrance product. In the prior art, isobutene and formaldehyde are generally subjected to Prins reaction in industrial production to prepare 3-methyl-3-alkene-1-butanol, then double bond isomerization is carried out to prepare 3-methyl-2-alkene-1-butanol, and then the 3-methyl-2-alkene-1-butanol is selectively oxidized to prepare the isopentenal. The Prins reaction between isobutene and formaldehyde in this synthetic route is carried out under severe conditions of ultra-high pressure and temperature (e.g. 250 ℃ C., 250Bar pressure); the isomerization reaction is carried out under severe limiting conditions using noble metal catalysts. In addition, the oxidation reaction from the prenyl alcohol to the prenyl aldehyde has the problems of high requirement on a catalyst, complex oxidation products, more byproducts, difficult separation and the like. In addition, the existing industrial production line of the iso-pentenal has the technical problems of large investment of industrial devices, low product yield, high cost and the like which need to be continuously improved.
As is well known, epoxy compounds are important basic chemical raw materials, have high reaction activity due to the existence of intramolecular ring tension, and are widely used in the fields of petrochemical industry, fine chemical industry, organic synthesis and the like. Under certain reaction conditions, the epoxy compound can undergo ring-opening carbonylation reaction. In the carbonylation ring-opening reaction of low-carbon epoxy compound, the hydroformylation reaction is always a research hotspot, and provides a cheap way to prepare beta-hydroxyaldehyde. For example, in the techniques disclosed in CN94191112 and CN95195314, the process of preparing β -hydroxyaldehyde from ethylene oxide by hydroformylation and then obtaining 1, 3-propanediol by hydrogenation has been industrialized. The beta-hydroxyaldehyde has multiple functional groups, and can be used for deriving various functional compounds. The hydroformylation of lower carbon epoxides provides a new potential route to the industry. However, the difficulty of hydroformylation of substituted epoxy compounds containing propylene or more is significantly increased, and since the epoxy compounds are relatively active, side reactions such as isomerization, reductive hydrogenation of carbonyl functional groups, dimerization of β -hydroxyaldehyde, and the like are often accompanied in the reaction process. There are few reports on the successful industrial application of substituted epoxy compounds of propylene or above to prepare the corresponding aldehydes by hydroformylation.
Aiming at the key technical problems of complex product, more byproducts, low product yield, harsh reaction, high cost and the like in the existing industrial production route of the isopentene aldehyde, the field needs to develop a new synthesis route of the isopentene aldehyde to solve the technical problems.
Disclosure of Invention
The invention provides a synthesis method of the isopropenal, which does not need harsh reaction conditions to solve the problems in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a synthesis method of isopentenal, which comprises the following steps: and performing hydroformylation reaction on epoxy isobutane to obtain hydroxyisovaleraldehyde, and performing intramolecular dehydration reaction on the hydroxyisovaleraldehyde to obtain the isopentenal.
In the synthesis method of the present invention, preferably, the hydroformylation reaction is carried out in the presence of a catalyst comprising a rhodium compound and an organophosphorus ligand. By adopting the combination application of the rhodium compound and the organophosphorus ligand, the complexation of the organophosphorus and the rhodium ions can better play a role of coordination with the rhodium ions, and the stability of the rhodium catalyst is improved. Further preferably, the mass ratio of the rhodium compound to the organophosphorus ligand is 1:10 to 1000, and more preferably 50 to 500. Preferably, the amount of the rhodium compound in the catalyst is 0.01-1%, preferably 0.02-0.1% relative to the total mass of the reaction system of the hydroformylation reaction, so as to obtain a better catalytic effect.
In the synthesis method of the present invention, preferably, the rhodium compound is selected from Rh (CO)2(acac)、RhCl3·3H2O、RhCl(CO)2、Rh4(CO)12、Rh6(CO)16And (RhNO)3)3One or more of (a). The combination application of the preferred rhodium compound and the organophosphorus ligand can better avoid side reactions of common epoxide isomerization, aldehyde condensation, hydrogenation and the like by using other metal catalysts, obviously improve the yield, and more preferably adopt the rhodium compound Rh (CO)2(acac)。
In the synthesis method of the present invention, preferably, the organophosphorus ligand may be selected from one or more of trialkyl phosphine, aryl phosphine, amino phosphine, carboxyl phosphine and organic phosphite, and the organic phosphite is selected from one or more of mono-organic phosphite, bi-organic phosphite and tri-organic phosphite. The activity of the catalyst and the selectivity of the reaction can be improved by using the preferred organophosphorus ligand in combination with the rhodium metal compound, particularly in combination with the preferred rhodium metal compound. In a preferred embodiment, the trialkylphosphine may preferably have an alkyl group having 4 to 12 carbons, and the alkyl group may be a cycloalkyl group.
In the synthesis method of the present invention, preferably, the organophosphorus ligand is an organophosphite, and more preferably, a triorganophosphite. More preferably, the organophosphite ester is a tri (substituted alkyl) phenyl phosphite. Still further preferred are tri (substituted alkyl) phenyl phosphites having the following structural formula (I):
wherein R in the formula (I)1-R3Are respectively and independently selected from linear alkyl of H, C1-C10, branched alkyl of C3-C10 or cycloalkyl with the carbon number less than or equal to 10. The organophosphite esters of formula (I) are preferably employed as organophosphorus ligands in the catalyst, have a multi-branching character, and promote an increase in catalytic activity.
In the synthesis method of the present invention, preferably, the organic phosphite is one or more selected from triphenyl phosphite, tris (2-tert-butyl-4-methylphenyl) phosphite, tris (2, 4-di-tert-butyl-6-methylphenyl) phosphite, tris (2-methyl-6-tert-butylphenyl) phosphite, tris (2, 4-di-tert-butylphenyl) phosphite and tris (2, 6-di-tert-butylphenyl) phosphite. The structural formula of the tris (2, 6-di-tert-butylphenyl) phosphite is shown as the following formula (II):
in the synthesis method of the present invention, preferably, the hydroformylation reaction is performed in the presence of a cocatalyst, the cocatalyst is a nitrogen-containing organic compound, and the nitrogen-containing organic compound is used as the cocatalyst, such that the selectivity of the epoxy ring-opening reaction can be improved, and the carbonyl group is more prone to attack the epoxy ring from the position with smaller steric hindrance. The cocatalyst is preferably selected from one or more of ethanolamine compounds, imidazole and imidazole derivatives or pyridine and pyridine derivatives. Further preferably, the cocatalyst is selected from one or more of 3-hydroxypyridine, 2- (dimethylaminomethyl) -3-hydroxypyridine, imidazole, ethanolamine, diethanolamine, and triethanolamine, and more preferably, the cocatalyst is selected from one or at least two of 2- (dimethylaminomethyl) -3-hydroxypyridine, and imidazole. Further preferably, the amount of the cocatalyst is 5-50%, preferably 10-20%, based on the total mass of the reaction system of the hydroformylation reaction.
In the synthesis method of the present invention, preferably, the hydroformylation reaction is performed in the presence of a polar organic solvent, and the polar organic solvent preferably includes one or more of tert-butyl alcohol, cyclohexanol, dimethyl ether, diethyl ether, ethylene glycol dimethyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, tetraethylene glycol methyl ether, alkylphenol polyoxyethylene ether, tetrahydrofuran, dimethoxyethane, methyl isobutyl ketone, and isophorone. More preferably alkylphenol ethoxylates, the alkylphenol ethoxylates is preferably (C4-C16) alkylphenol ethoxylates, and more preferably octylphenol polyoxyethylene. The introduction of polyoxyethylene ether groups can provide a gas to synthesis (CO/H)2) The solubility of the hydroformylation organic substrate in a system can be increased, the contact degree of the organic substrate and the synthesis gas can be increased, and the reaction efficiency can be improved.
In the synthesis method of the invention, preferably, the epoxy isobutane contains CO and H2The hydroformylation reaction occurs.
In the synthesis method of the present invention, preferably, the hydroformylation reaction conditions include: at 20-200 deg.C and 1-20MPa, CO and H2The molar ratio of (1: 5) - (5: 1); further preferably, the temperature is 50-150 ℃, the pressure is 3-10MPa, and CO and H2In a molar ratio of 1:2 to 2: 1.
In the synthesis method of the present invention, preferably, the intramolecular dehydration reaction is carried out in the absence of a catalyst or in the presence of a catalyst. The dehydration reaction may be promoted by conducting the dehydration in the presence of a catalyst, preferably selected from one or more of sulfuric acid, phosphoric acid, p-toluenesulfonic acid, solid acid catalysts, such as one or more of acidic ion exchange resins, molecular sieves, heteropolyacids, and the like. The amount of the catalyst used is preferably 0.1% to 20% of the total mass of the reaction raw materials used for dehydration. In the synthesis method of the invention, the intramolecular dehydration reaction of the hydroxyisovaleraldehyde is preferably carried out without a catalyst, and the direct thermal cracking is carried out without a catalyst, so that the generation of aldehyde side reaction caused by the adoption of a catalyst (such as strong acid) is avoided, and the corrosion of reaction on equipment materials and the problem of three-waste treatment caused by the corrosion can be avoided. Preferably, when the intramolecular dehydration is carried out in the absence of a catalyst, the hydroxyisovaleraldehyde is thermally cracked under the following conditions to produce the isoprenal: the temperature is 100-300 ℃, the pressure is 1-10BarA, and the reaction time is 120 hours; preferably, the temperature is 150 ℃ and 250 ℃, the pressure is 1-5BarA, and the reaction time is 2-10 hours. When the dehydration is carried out in the presence of a catalyst, it is preferably carried out under the following conditions: the temperature is 50-300 ℃, the pressure is 1-10BarA, and the reaction time is 0.1-10 hours; preferably, the temperature is 100 ℃ and 200 ℃, the pressure is 1-5BarA, and the reaction time is 0.2-5 hours. In the specific implementation process, the generated water is preferably removed from the reaction system in time by means of reaction rectification and the like, so that chemical equilibrium is promoted, and the reaction yield is further improved.
The synthesis method of the present invention preferably further comprises the following steps: and (2) carrying out epoxidation reaction on a material containing isobutene and peroxide to obtain the epoxy isobutane. Further preferably, the epoxidation reaction takes place in the presence of a catalyst. In order to obtain a higher reaction yield, the catalyst is preferably selected from molybdenum salts of molybdenum having a chemical valence of 4 to 6, more preferably from MoO3、Mo(CO)5、MoCl5、MoO2(acac)2More preferably MoO2(acac)2Acac refers to acetylacetone group, and the introduction of organic coordination groups can improve the contact effect of reaction raw materials and remarkably improve the reaction efficiency. Preferably, the catalyst is used in an amount of 0.01 to 0.1% based on the total mass of the reaction system for the epoxidation reaction. The reaction conditions of the epoxidation reaction preferably include: the temperature is 20-200 ℃, the pressure is 0.1-10MPa, the reaction time is 1-20 hours, and the mass ratio of the peroxide to the isobutene is 1:2-2: 1; further preferably, the temperature is 50-150 ℃ and the pressure is0.5-5MPa, and the reaction time is 2-10 hours. Preferably, the peroxide comprises one or more of hydrogen peroxide, peroxy phenylethane, peroxy-isopropyl benzene, tert-butyl hydroperoxide and peroxy acid, more preferably tert-butyl hydroperoxide. In a more preferred embodiment, t-butyl hydroperoxide is preferably used as the peroxide, and MoO is preferably used2(acac)2As a catalyst, a better reaction yield can be obtained.
The pressure in the present invention is absolute pressure unless otherwise specified.
For the purpose of facilitating understanding of the synthetic route of the present invention, the following is illustrative of the main reaction route in one embodiment, and is herein intended to be exemplary and not limiting:
the technical scheme provided by the invention has the following beneficial effects:
the synthesis method provided by the invention avoids harsh process conditions of the existing industrial route, can obtain the target product at high yield under mild conditions, and further provides a new route selection for synthesizing prenol, citral, vitamin A, vitamin E and the like by using prenylaldehyde.
Drawings
FIG. 1 is a mass spectrum of epoxy isobutane;
FIG. 2 is a mass spectrum of the iso-pentenal.
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.
In the following examples or comparative examples, the reaction effect was calculated by quantitative analysis of the raw materials and products by gas chromatography under the following conditions:
a chromatographic column: shimadzu HP-PONA (specification 50 m.times.0.2 mm.times.0.25 μm); sample inlet temperature: 280 ℃; the split ratio is as follows: 50: 1; flow rate of column: 0.5 ml/min; temperature rising procedure: keeping at 40 deg.C for 8min, and heating to 240 deg.C at 10 deg.C/min; detector temperature: 300 ℃; h2Flow rate: 40 ml/min; air flow rate: 400 ml/min.
The reagents used in the following examples or comparative examples are illustrated below: isobutene and tert-butyl hydroperoxide TBHP are from the Wanhua tobacco industry park, and the purity is 99 percent. Reagents other than the sources indicated in the examples were purchased from the reagent Aladdin, and analyzed for purity.
Example 1
This example for the preparation of isopentenal includes the following steps:
(1) preparing epoxy isobutane: into the autoclave were charged 150g of isobutylene and 1g of MoCl55g of ethylene glycol, 300g of tert-butyl hydroperoxide (TBHP), N-charged2The reaction is carried out for 4 hours at 120 ℃ under the pressure of 0.5 Mpa. The yield of the product epoxy Isobutane (IBO) is 90 percent. 172g of epoxy isobutane with the purity of 99.5% is obtained for standby through rectification and separation, and a mass spectrum chart of the epoxy isobutane is shown in an attached figure 1.
(2) 10g of the previously prepared epoxy isobutane was taken and added into a 500ml pressure stirring reaction kettle, the reaction temperature was 125 ℃, the synthetic gas pressure was 8MPa, and the reaction pressure was CO: h2Volume ratio (i.e., molar ratio) 2:1, with 0.1gRh (CO)2(acac) and 10g of tris (2, 4-di-tert-butylphenyl) phosphite (purity 98%) produced in the chemical industry from Zibo zixiang as a catalyst (molar ratio of rhodium compound to organic phosphite is about 1:40), 150g of octylphenol polyoxyethylene ether (CAS: 9036-19-5) as a solvent without adding a cocatalyst, and reacting for 24 hours. The conversion rate of epoxy isobutane is about 45%, the selectivity of hydroxyisovaleraldehyde is about 70%, and the nuclear magnetic results of hydroxyisovaleraldehyde are as follows:1H NMR(400MHz,CDCl3)1.24(s,6H)2.07(d,J＝6.20Hz,2H)3.65(s,1H)5.02-5.07(m,2H)5.82(m,1H)。
(3) decompressing the reaction kettle in the step (2) to normal pressure, and using N2The displacement was carried out 3 times, and the reaction solution was distilled to remove the catalyst and unconverted starting materials. Adding 8g of the obtained product mixed solution into a 150ml three-neck flask, taking 20g of A-45 strong acid ion exchange resin of Dow company as a catalyst and 50g of cyclohexane as a water carrying agent, arranging a condensing tube and a water separator with circulating cooling water on the flask, heating and refluxing for 5h in an oil bath at normal pressure and 120 ℃, taking outGC analysis is carried out on the residue liquid, the conversion rate of hydroxyisovaleraldehyde is 90%, the selectivity of isopentenal is 65%, and the mass spectrum of the isopentenal is shown in figure 2.
Example 2
This example for the preparation of isopentenal includes the following steps:
(1) the procedure was the same as in (1) of example 1;
(2) this step is substantially the same as step (2) in example 1, except that 20g of 2- (dimethylaminomethyl) -3-hydroxypyridine as a co-catalyst was added in step (2) in this example. The conversion rate of the epoxy isobutane obtained in the step (2) is 71%, and the selectivity of the hydroxyl isovaleraldehyde is about 76%.
(3) Step (3) of this example was substantially the same as step (3) of example 1, except that 2g of p-toluenesulfonic acid was used as a catalyst in this example instead of the strongly acidic ion exchange resin in example 1, and the reaction was heated at 120 ℃ and refluxed for 3 hours. By GC analysis, the conversion of hydroxyisovaleraldehyde was 87% and the selectivity to isovalerenal was 63%.
Example 3
This example for the preparation of isopentenal includes the following steps:
(1) preparing epoxy isobutane: into the autoclave were charged 150g of isobutylene and 0.1g of MoO2(acac)210g of ethylene glycol, 170g of tert-butyl hydroperoxide (TBHP), N-charged2The reaction is carried out for 4 hours at 90 ℃ under the pressure of 2 Mpa. The yield of the product epoxy Isobutane (IBO) is 96 percent. 130g of epoxy isobutane with the purity of 99.5 percent is obtained by rectification and separation for standby.
(2) Adding 20g of 2, 6-di-tert-butylphenol into a reaction kettle, wherein a condensation pipe with circulating condensed water is arranged on the reaction kettle, controlling the reaction temperature to be 190-200 ℃ after heating and melting, and introducing N2Bubbling operation, namely, dropwise and slowly adding 50g of phosphorus trichloride (after dropwise addition within 1 h) under stirring for reaction; after the addition, the reaction was continued for 3 hours. After the reaction was completed, the reaction solution was washed three times with 40g of ethanol each time to remove unreacted 2, 6-di-t-butylphenol, and then washed three times with 40g of water each time to remove phosphorus trichloride and hydrogen chloride. Dissolving the obtained product in 50g of ethylene glycol dimethyl ether, evaporating, crystallizing, filtering, repeatedly recrystallizing for three times to obtain tris (2, 6-di-tert-butylphenyl) phosphiteThe above operations are repeated to prepare 30g of finished product for later use, wherein the finished product is 8 g. Nuclear magnetic results for tris (2, 6-di-tert-butylphenyl) phosphite:1H NMR(400MHz,CDCl3)1.35(s,54H)7.07-7.09(m,9H)。
(3) 10g of the previously prepared epoxy isobutane was taken and added into a 500ml pressure stirring reaction kettle, the reaction temperature was 125 ℃, the synthetic gas pressure was 18MPa, and the reaction pressure was CO: h2Volume ratio (i.e., molar ratio) 2:1, with 0.1gRh (CO)2(acac), 30g of tris (2, 6-di-tert-butylphenyl) phosphite as a catalyst (molar ratio of rhodium compound to organic phosphite: about 1:120), 20g of 2- (dimethylaminomethyl) -3-hydroxypyridine as a co-catalyst, and 150g of octylphenol polyoxyethylene ether (CAS: 9036-19-5) as a solvent were reacted for 24 hours. The conversion rate of epoxy isobutane is about 65%, and the selectivity of hydroxyisovaleraldehyde is about 85%.
(4) Depressurizing the reaction kettle in the step (3) to normal pressure, and using N2The displacement was carried out 3 times, and the reaction solution was distilled to remove the catalyst and unconverted starting materials. Adding 8g of the obtained product mixed solution into a 150ml three-neck flask, taking 50g of cyclohexane as a water carrying agent, arranging a condensing tube and a water separator with circulating cooling water on the three-neck flask, heating and refluxing for 5 hours in an oil bath at the temperature of 170 ℃ under normal pressure, taking the kettle liquid for GC analysis, and obtaining the conversion rate of hydroxyl isovaleraldehyde>80% Isopentenal selectivity>85％。
As can be seen from the examples 1 and 2, when the epoxy isobutane is subjected to hydroformylation reaction to prepare the hydroxyisovaleraldehyde, the co-catalyst is added, and the conversion rate and the selectivity of the obtained target product are both remarkably improved compared with the case that the co-catalyst is not added. As can be seen from the above examples, the selectivity of the target product obtained without using a catalyst is higher in the intramolecular dehydration reaction. From the above examples, it can be seen that, when the catalyst system of the present invention combining rhodium compound and organophosphorus ligand is used to prepare hydroxyisovaleraldehyde by hydroformylation of epoxy isobutane, the selectivity is all over 70%, and better conversion rate is obtained, while example 3 using tris (2, 6-di-tert-butylphenyl) phosphite as organophosphorus ligand has better effect, and higher conversion rate and selectivity are obtained at the same time. It can be seen from the above examples that the synthesis route for preparing the isopropenal of the present invention requires mild reaction conditions, and has high conversion rate and high selectivity of the target product, and thus, has high product yield.
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 (31)
1. A method for synthesizing the isopentenal is characterized by comprising the following steps: performing hydroformylation reaction on epoxy isobutane to obtain hydroxyisovaleraldehyde, performing intramolecular dehydration reaction on the hydroxyisovaleraldehyde to obtain the isopentenal,
the hydroformylation reaction is carried out in the presence of a catalyst comprising a rhodium compound and an organophosphorus ligand;
the rhodium compound is selected from Rh (CO)2(acac)、RhCl3·3H2O、RhCl(CO)2、Rh4(CO)12、Rh6(CO)16And (RhNO)3)3One or more of (a) or (b),
the organophosphorus ligand is a tri (substituted alkyl) phenyl phosphite having the following structural formula (I):
wherein R in the formula (I)1-R3Are respectively and independently selected from linear alkyl of H, C1-C10, branched alkyl of C3-C10 or cycloalkyl with the carbon number less than or equal to 10.
2. The method of synthesis according to claim 1,
the mass ratio of the rhodium compound to the organophosphorus ligand is 1: 10-1000.
3. The synthesis process according to claim 2, characterized in that the mass ratio between the rhodium compound and the organophosphorus ligand is 1: 50 to 500.
4. The synthesis method according to claim 1, wherein the amount of the rhodium compound used in the catalyst is 0.01 to 1% by mass based on the total mass of the reaction system for the hydroformylation reaction.
5. A synthesis process according to any one of claims 1 to 4, characterised in that the organophosphorus ligand is selected from one or more of triphenyl phosphite, tris (2-tert-butyl-4-methylphenyl) phosphite, tris (2, 4-di-tert-butyl-6-methylphenyl) phosphite, tris (2-methyl-6-tert-butylphenyl) phosphite, tris (2, 4-di-tert-butylphenyl) phosphite and tris (2, 6-di-tert-butylphenyl) phosphite.
6. The synthesis process according to claim 1, characterized in that the hydroformylation reaction is carried out in the presence of a co-catalyst which is a nitrogen-containing organic compound.
7. A synthesis method according to claim 6, characterized in that the cocatalyst is one or more selected from ethanolamine compounds, imidazole and imidazole derivatives, or pyridine and pyridine derivatives.
8. The synthesis method of claim 6, wherein the cocatalyst is selected from one or more of 3-hydroxypyridine, 2-dimethylaminomethyl-3-hydroxypyridine, imidazole, ethanolamine, diethanolamine, and triethanolamine.
9. The synthesis method according to claim 6, wherein the amount of the cocatalyst is 5-50% based on the total mass of the hydroformylation reaction system.
10. The synthesis method according to claim 9, wherein the amount of the cocatalyst is 10-20% based on the total mass of the hydroformylation reaction system.
11. The synthesis process according to any one of claims 1 to 4, wherein the hydroformylation reaction is carried out in the presence of a polar organic solvent comprising one or more of tert-butanol, cyclohexanol, dimethyl ether, diethyl ether, ethylene glycol dimethyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, tetraethylene glycol methyl ether, alkylphenol ethoxylates, tetrahydrofuran, dimethoxyethane, methyl isobutyl ketone and isophorone.
12. The method of claim 11, wherein the alkylphenol ethoxylate is a C4-C16 alkylphenol ethoxylate.
13. The method of claim 11, wherein the alkylphenol ethoxylate is octylphenol ethoxylate.
14. Synthesis method according to any one of claims 1 to 4, characterized in that the epoxyisobutane is reacted with a catalyst containing CO and H2The hydroformylation reaction occurs.
15. The synthesis process according to any one of claims 1 to 4, characterized in that the conditions of the hydroformylation reaction comprise: at 20-200 deg.C and 1-20MPa, CO and H2The molar ratio of (A) to (B) is 1:5-5: 1.
16. The synthesis process of claim 15, wherein the hydroformylation reaction conditions include: at 50-150 deg.C and 3-10MPa, CO and H2In a molar ratio of 1:2 to 2: 1.
17. The synthesis method according to any one of claims 1 to 4, characterized in that the intramolecular dehydration reaction is carried out in the absence of a catalyst or in the presence of a catalyst; the catalyst is selected from one or more of sulfuric acid, phosphoric acid, p-toluenesulfonic acid and solid acid catalysts.
18. The synthesis method according to claim 17, wherein the catalyst for the intramolecular dehydration reaction is used in an amount of 0.1 to 20% by mass based on the total mass of the reaction raw materials used for the intramolecular dehydration reaction.
19. A synthesis process according to claim 17, characterised in that the solid acid catalyst is selected from one or more of acidic ion exchange resins, molecular sieves and heteropolyacids.
20. The synthesis method of claim 17, wherein the intramolecular dehydration reaction is carried out in the absence of a catalyst, and the hydroxyisovaleraldehyde is thermally cracked under the following conditions to obtain the isopentenal: the temperature is 100 ℃ and 300 ℃, the pressure is 1-10BarA, and the reaction time is 1-20 hours.
21. The method of claim 20, wherein said hydroxyisovaleraldehyde is thermally cracked to produce said pentenal in the absence of a catalyst during said intramolecular dehydration reaction: the temperature is 150 ℃ and 250 ℃, the pressure is 1-5BarA, and the reaction time is 2-10 hours.
22. The synthesis method according to claim 17, characterized in that the intramolecular dehydration reaction is carried out in the presence of a catalyst under the following conditions: the temperature is 50-300 ℃, the pressure is 1-10BarA, and the reaction time is 0.1-10 hours.
23. The synthesis method according to claim 22, characterized in that the intramolecular dehydration reaction is carried out in the presence of a catalyst under the following conditions: the temperature is 100 ℃ and 200 ℃, the pressure is 1-5BarA, and the reaction time is 0.2-5 hours.
24. The method of synthesis according to any one of claims 1 to 4, further comprising the steps of: and (2) carrying out epoxidation reaction on a material containing isobutene and peroxide to obtain the epoxy isobutane.
25. The synthesis method according to claim 24, wherein the epoxidation reaction takes place in the presence of a catalyst selected from the group consisting of molybdenum salts of which the chemical valence of molybdenum is from 4 to 6.
26. The synthesis method according to claim 25, characterized in that the catalyst is chosen from MoO3、Mo(CO)5、MoCl5、MoO2(acac)2One or more of.
27. The synthesis method according to claim 25, wherein the catalyst is used in an amount of 0.01 to 0.1% based on the total mass of the reaction system for the epoxidation reaction.
28. The synthesis method of claim 24, wherein the reaction conditions of the epoxidation reaction comprise: the temperature is 20-200 ℃, the pressure is 0.1-10MPa, and the reaction time is 1-20 hours.
29. The method of synthesis of claim 24, wherein the mass ratio of peroxide to isobutylene is from 1:2 to 2: 1.
30. The synthesis method of claim 24, wherein the reaction conditions of the epoxidation reaction comprise: the temperature is 50-150 ℃, the pressure is 0.5-5MPa, and the reaction time is 2-10 hours.
31. The method of synthesizing as defined in claim 24 wherein the peroxide comprises one or more of hydrogen peroxide, peroxy-phenylethane, peroxy-cumene, t-butyl hydroperoxide and peroxy acids.
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| CN1056678A (en) * | 1990-05-04 | 1991-12-04 | 联合碳化化学品及塑料技术公司 | Be used to produce 1, the catalyzer and the method for 3-glycol and/or 3-hydroxy aldehyde |
| CN1117289A (en) * | 1993-02-05 | 1996-02-21 | 国际壳牌研究有限公司 | Process for making 1,3-diols and 3-hydroxyaldehydes |
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