CN109134538B - Iodophosphine oxide ligands, method for the production thereof, complexes, catalyst systems comprising the complexes and use thereof - Google Patents
Iodophosphine oxide ligands, method for the production thereof, complexes, catalyst systems comprising the complexes and use thereof Download PDFInfo
- Publication number
- CN109134538B CN109134538B CN201811112669.4A CN201811112669A CN109134538B CN 109134538 B CN109134538 B CN 109134538B CN 201811112669 A CN201811112669 A CN 201811112669A CN 109134538 B CN109134538 B CN 109134538B
- Authority
- CN
- China
- Prior art keywords
- compound
- potassium
- cesium
- catalyst
- reaction
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5325—Aromatic phosphine oxides or thioxides (P-C aromatic linkage)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/245—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of keto groups or secondary alcohol groups
Abstract
The invention relates to an iodophosphine oxide ligand, a preparation method thereof, a complex, a catalyst system comprising the complex, a method for preparing isooctanoic acid by oxidizing isooctyl aldehyde and application of the catalyst system. The invention not only can overcome the defect of poor selectivity in the prior art, but also has the advantages of mild process, simple and convenient ligand preparation, high activity and small dosage.
Description
Technical Field
The invention relates to an iodophosphine oxide ligand, a preparation method and a complex thereof, a catalyst system comprising the complex, and a method and application thereof for preparing isooctanoic acid by oxidizing isooctyl aldehyde.
Background
2-Ethylhexanoic Acid (EHA), also known as isooctanoic Acid in Chinese, is an oily liquid that is slightly soluble in cold water and ethanol, dissolved in hot water and diethyl ether. It features high purity and light lustre. Can react with various metal compounds to generate metal salts of isooctanoic acid, and has the following main applications: the paint drying agent, lubricating oil assistant, plastic plasticizer, PVC stabilizer, medical salt forming agent and reaction catalyst assistant.
At present, China is the second largest world paint producing country second to the United states, particularly, high-grade paints are developed rapidly, in addition, the synthetic resin and unsaturated polyester industries of China are developed rapidly, high-grade ink is developed rapidly, isooctanoic acid and salt substances thereof are used more widely in the industries, and the market prospect of isooctanoic acid and isooctanoic acid salt is expected to be very good in the coming years.
The isooctanoic acid industrial synthesis mainly comprises two routes, one is isooctanol oxidation method, although the method has high selectivity and reliable and simple operation of raw material source, the process flow is long, and the large-scale production is not easy, so that the currently domestic biggest isooctanoic acid supplier Shenyang Zhangming chemical industry and devices of Picheng Qianjie technology Limited company in Piancheng adopt the route for production; secondly, n-butyl aldehyde is used as a raw material, 2-ethyl hexenal is generated through condensation and dehydration, isooctyl aldehyde is obtained through hydrogenation, and isooctyl acid is obtained through oxidation. The aldehyde oxidation process has reliable raw material sources, is a continuous and totally-enclosed process, is easy for large-scale production, and is mostly adopted by some major companies in Europe and America.
The reaction equation for preparing isooctanoic acid by oxidizing isooctylaldehyde is as follows:
patent CN1357527A discloses a method for producing 2-ethyl hexanoic acid, which discloses an optimal reaction temperature of 0-15 ℃ and a maximum selectivity of 94.9%, but the engineering temperature control energy consumption is high, and the industrialization is not ideal. Patent CN1410407A discloses a method for producing 2-ethyl hexanoic acid, which overcomes the disadvantages of the above patent and improves the optimum reaction temperature to 30-50 ℃, and the reaction equipment is changed from a bubble column to a falling film reactor, but the investment cost of industrial production equipment is high, and the selectivity is not obviously improved. Patent CN1422840A discloses a 2-ethyl groupThe said patent changes the reaction equipment into reaction tower, greatly shortens reaction time, and has the highest selectivity of 96.8%, but the post-treatment of catalyst is troublesome. The above 3 patents are all published by the company Qilu petrochemical company, and the catalyst used is Mn (OAc)2Or KOAc or Cu (OAc)2Or NaOAc or a mixture of these four substances in any ratio, the selectivity is not very satisfactory and no work-up of the catalyst is reported.
Patent CN102701944A discloses a method for preparing 2-ethyl hexanoic acid by catalyzing and oxidizing 2-ethyl hexanal with phosphomolybdovanadate. The patent relates to a preparation method of a chemical preparation, the selectivity of 2-ethyl hexanoic acid can reach more than 98%, but the preparation of the catalyst needs molybdate, phosphate, metavanadate, concentrated sulfuric acid, hydrochloric acid and the like, the preparation process is complex, the regeneration is difficult, and the catalyst has a long distance from industrial application.
Patent US5739352 discloses a process for preparing carboxylic acids by oxidizing aldehydes with peracids in the presence of amines or amine-N-oxides as catalysts. The catalyst used comprises substituted or unsubstituted alkylamines, alkylamine-N-oxides, or aromatic amines, aromatic amine-N-oxides or mixtures thereof. But has the defects that the boiling point of the catalyst containing the N element is very high, the post-treatment is relatively complex, and the requirement on reaction equipment is relatively high.
Patent WO2001046111A discloses an oxidation process which is generally carried out at moderate temperatures and low pressures. The main feature of this patent is the use of a higher shear energy system with large volume at high turbulence levels, which increases mass transfer efficiency, and the addition of less than 2.0 wt% of an inhibitor such as alkali metal salts of 2-ethylhexanoic acid potassium salt, etc. for improved selectivity without the addition of metal catalysts or free radical initiators, but the process of this patent has a selectivity of only 96.4% at best for the oxidation of 2-ethylhexanol.
In summary, the prior art discloses that the homogeneous catalyst or the technology for preparing isooctanoic acid from isooctylaldehyde is difficult to separate (Mn (OAc))2Or KOAc or Cu (OAc)2Etc.), or the catalyst preparation process is cumbersome and highly corrosive, orComplex process, non-ideal product selectivity and the like.
It is generally recognized in the art that liquid phase gas oxidation of isooctylaldehyde is a classical chain radical reaction involving initiation, extension, and termination of the chain. The general reaction mechanism is known from the literature as follows:
the oxidation reaction of aldehyde into carboxylic acid mainly comprises two stages, firstly, aldehyde is converted into peracid and then undergoes an affinity addition reaction with aldehyde to generate a Criegee intermediate; second, the latter has two pathways to decompose, the A pathway is the migration of the hydrogen on the aldehyde carbonyl group to the nearest oxygen atom to form two molecules of carboxylic acid, the B pathway is the migration of the R group on the aldehyde carbonyl group to the nearest oxygen atom to form one molecule of carboxylic acid and one molecule of formate ester, which is eventually hydrolyzed to formic acid and alcohol, which is further oxidized to ketone. The a pathway is the predominant mechanism in most reactions. The oxidation of aldehydes to the corresponding carboxylic acids is important in connection with the formation of aldehydes, and generally linear aliphatic aldehydes have high selectivity, while aldehydes having alpha branches easily cause side reactions, resulting in a decrease in selectivity. The Mn salt or Co salt in the prior art accelerates the initiation of radicals to cause an increase in side reactions. The complex of iodophosphine oxide ligand and cesium in the present invention can not only promote the reaction of the peroxy intermediate to path A but also suppress the progress of side reactions, because of the specificity of the results. The ligand has extremely high activity, iodine in the structure has great steric hindrance, and the rigidity of the catalyst structure is increased, so that the migration of an R group in a path B path can be prevented, the regional selectivity of the reaction is improved, and the selectivity of a product is further improved.
Disclosure of Invention
The invention aims to provide a novel method for preparing isooctanoic acid by catalytic oxidation of isooctaldehyde, which can obtain ideal selectivity and yield and is suitable for industrialization. Compared with the prior art, the catalyst has the advantages of small dosage, high catalytic efficiency and high product selectivity.
According to a first aspect of the present invention there is provided an iodophosphine oxy ligand of the general formula:
wherein R1-R10 each independently represent a group selected from CF3F, Br or selected from CH3、OCH3、CH(CH3)3The electron-donating functional group in (1) is preferably R1 ═ R4, R2 ═ R3, R6 ═ R9, R8 ═ R5, or R7 ═ R10.
The preferred iodophosphine oxide ligands in the present invention are one or more of L1-L9, preferably L6 and/or L8, L1-L9 have the following structural formula:
the electron withdrawing group on the benzene ring can reduce the electron cloud density of the whole structure, the electron cloud density of the whole structure is improved due to the insecure coordination with metal cesium and low catalytic activity, and the electron donating group can improve the electron cloud density of the whole structure, is more tightly coordinated with the empty orbit of the metal cesium and improves the catalytic activity. The ligand can be synthesized by adopting an organic chemical method, and the specific synthetic steps are shown in the specific embodiment.
According to a second aspect of the present invention, there is provided a process for preparing the above iodophosphine oxide ligand, comprising the steps of:
reacting compound 1 and compound 2 in CuI and Na2CO3Synthesizing an iodophosphine oxide ligand under the action of acetone:
the structural formulas of compound 1 and compound 2 are as follows:
compound 1And compound 2 can be synthesized in an organic synthesis method or purchased from the market. Wherein R11-R12 each independently represent a group selected from CF3F, Br or selected from CH3、OCH3、CH(CH3)3Electron donating functional groups in (1).
In the above preparation method, the molar ratio of compound 1 to compound 2 may be 1:0.5 to 1.5, preferably 1:0.8 to 1.2.
In the preparation of the iodophosphine oxide ligand of the present invention, the amount of CuI added is 0.1 to 0.6 wt%, preferably 0.2 to 0.4 wt%, of the total amount of the compound 1 and the compound 2.
In the preparation of the iodophosphine oxide ligand of the present invention, Na2CO3The ratio of the added molar amount of (b) to the total molar amount of the compound 1 and the compound 2 is 1:1 to 4:1, preferably 1:1 to 2: 1.
In the preparation of the iodophosphine oxide ligand of the present invention, the ratio of the volume of acetone added (V/mL) to the total mass of compound 1 and compound 2 is 1.5:1 to 4:1, preferably 1.5:1 to 2: 1.
In the preparation of the iodophosphine oxide ligand, the reaction temperature is normal temperature (ambient temperature), and the reaction is carried out under normal pressure.
In the preparation of the iodophosphine oxide ligand, the reaction time is 6-12h, preferably 6-8 h.
In the preparation of the iodophosphine oxide ligand, ethyl acetate and water are used for extraction reaction after the reaction is finished, anhydrous sodium sulfate is dried, reduced pressure concentration is carried out, and column chromatography is carried out to obtain the target ligand.
According to a third aspect of the present invention, there is provided a complex of the above iodophosphinyl oxygen ligand with cesium. It can be prepared by mixing the above iodophosphino ligands with a source of metal cesium such as one or more of cesium carbonate, cesium hydroxide, cesium acetate, cesium nitrate (preferably cesium carbonate).
According to a fourth aspect of the present invention, there is provided a catalyst system comprising a catalyst and a promoter, wherein the promoter is a potassium salt, the catalyst is a complex of iodophosphine oxide ligand and cesium, and the ligand has the general structural formula:
wherein R1-R10 each independently represent a group selected from CF3F, Br or selected from CH3、OCH3、CH(CH3)3The electron-donating functional group in (1) is preferably R1 ═ R4, R2 ═ R3, R6 ═ R9, R8 ═ R5, or R7 ═ R10.
The potassium salt may be one or more selected from potassium nitrate, potassium carbonate, potassium chloride, potassium sulfate, potassium hydrogen sulfate, potassium phosphate, potassium hydroxide, potassium iodide, potassium acetate, potassium bromide, and potassium fluoride, preferably potassium acetate.
The source of cesium metal in the catalyst of the present invention can be one or more of cesium carbonate, cesium hydroxide, cesium acetate, and cesium nitrate, with cesium carbonate being preferred.
The catalyst promoter can be one or more of potassium nitrate, potassium carbonate, potassium chloride, potassium sulfate, potassium bisulfate, potassium phosphate, potassium hydroxide, potassium iodide, potassium acetate, potassium bromide and potassium fluoride, and preferably potassium acetate.
Preferably, the molar ratio of cesium to iodophosphine oxide ligand in the catalyst of the present invention is from 1:1 to 10:1, preferably from 5:1 to 8: 1.
According to a fifth aspect of the present invention, there is further provided a process for the oxidation of isooctylaldehyde to produce isooctanoic acid, the process comprising: in the presence of the catalyst system comprising the complex catalyst of the iodophosphine oxide ligand and cesium and the catalyst auxiliary agent potassium salt, isooctylaldehyde is oxidized in an oxygen-containing gas atmosphere to obtain isooctanoic acid.
Preferably, the isooctanoic acid is prepared by mixing 2-ethylhexanal with a solvent and using the mixture as a reaction raw material. The solvent can dilute the concentration of reactant aldehyde, which is beneficial to heat dissipation and properly reduces the reaction rate. The mass fraction of 2-ethylhexanal in the reaction raw material is 25-50 wt%, preferably 35-45 wt%. The solvent is n-octanoic acid or 2-ethyl hexanoic acid, or a mixed solvent composed of the n-octanoic acid or the 2-ethyl hexanoic acid in any proportion, and 2-ethyl hexanoic acid is preferred, so that the step of solvent separation can be omitted.
The mass fraction of the iodophosphine oxide ligand and cesium complex catalyst in the present invention relative to the reaction raw material 2-ethylhexanal may be 100-600ppm, preferably 100-500 ppm.
The mass percentage range of the catalyst promoter sylvite in the reaction raw material 2-ethylhexanal is 0.1-0.6 wt%, preferably 0.2-0.5 wt%.
In the method for preparing isooctanoic acid of the present invention, the oxygen-containing gas can be pure oxygen, air, or oxygen-enriched gas composed of inert gas (preferably nitrogen) and oxygen, and air is preferred in view of the requirement of the concentration of the process safety tail oxygen.
In the method for producing isooctanoic acid of the present invention, the molar ratio of isooctylaldehyde to oxygen is 1:0.5 to 1:1.0, and from the viewpoint of tail oxygen concentration and reaction selectivity, it is preferably 1:0.6 to 1: 0.8.
The reaction for preparing the isooctanoic acid by oxidizing the isooctyl aldehyde is exothermic reaction, the temperature cannot be accurately controlled, but in order to reduce the environmental conditions required by the reaction and reduce the cost, the reaction is carried out at normal temperature, the reaction temperature can be controlled to be 10-50 ℃, preferably 20-35 ℃, most preferably 30-35 ℃, and the heat can be taken away by cooling water in a coil outside the device.
In the preparation method of the isooctanoic acid, the reaction time is 3-9h, preferably 6-8 h.
The invention also provides the application of the catalyst system as a catalyst for preparing isooctanoic acid by oxidizing isooctaldehyde.
The invention has the following positive effects:
the process has the advantages of mild reaction conditions, simple and convenient catalyst preparation, high catalytic activity, effective inhibition of side reactions, high product selectivity and few three wastes.
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are not intended to limit the scope of the invention.
Iso-octanal (> 95%) was purchased from echiei (shanghai) chemical industry development limited; isooctanoic acid, dichloromethane, KI, sodium nitrate, tetrahydrofuran were purchased from the avastin reagent;
tert-butyl lithium, trifluoroacetic acid, diethyl ether, ethyl formate, potassium salt, cesium salt were purchased from carbofuran reagent;
starting materials for the preparation of both compound 1 and compound 2 are commercially available.
Gas chromatograph: agilent7890, chromatographic column SH-RTX-WAX, method: temperature programming, tail-blow flow: 30mL/min, hydrogen flow: 40mL/min, air flow: 400mL/min, the split ratio is 30: 1; temperature rising procedure: from 60 ℃ to 80 ℃ at a rate of 20 ℃/min, and then to 250 ℃ over 8min, the total program time: 23.3min, detector temperature: at 260 ℃. The data analysis method comprises the following steps: area normalization method.
The calculation formulas of conversion rate, selectivity and yield are as follows:
conversion rate:
and (3) selectivity:
yield: XS ═ Y
a0Is the initial concentration of isooctanalReaction ofIs the concentration after the reaction of isooctylaldehyde, b0Is the initial concentration of 2-ethylhexanoic acid, bReaction ofIs the concentration of isooctanoic acid after the reaction.
Example 1: preparation of compound 1(R1 ═ OCH3)
Compound 3(22.3g, 0.1mol) was dissolved in 200mL of redistilled THF in a 500mL three-necked flask, ethyl formate (3.7g,0.05mol) was slowly added at 0 deg.C, after which time stirring was continued for 30min, then t-BuLi (87mL, 1M in THF, 87mmol) was slowly added dropwise at 0 deg.C, and stirring was continued for 3 h. After the reaction was completed, the reaction was quenched with water, and then extracted with ethyl acetate, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and subjected to column chromatography to give compound 4(39.5g, 83%) as an oily product.
Compound 4(23.7g, 0.05mol) was dissolved in 200mL of redistilled DCM in a 500mL three-necked flask, and TFA (11.4mL, 0.15mol) was added at 50 ℃ and stirring was continued for 6h after the addition was complete. After the reaction was completed, the reaction mixture was concentrated under reduced pressure, and the obtained product was used in the next reaction without further purification. Dissolving the obtained product with 50mL of concentrated hydrochloric acid, slowly adding NaNO3(25.5g, 0.3mol) at-10 ℃, heating to 0 ℃ after adding, reacting for 2H, and then adding KI (49.8g, 0.3mol) and H2O1L, the reaction was stirred at room temperature for 2h, after which the reaction was quenched with 50g of sodium thiosulfate. Then, the reaction mixture was extracted with ethyl acetate and water, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and subjected to column chromatography to give compound 5(15g, 63%) as an oily product.
Compounds of the other groups in Compound 1 were synthesized according to this method.
Example 2: preparation of compound 2(R5 ═ R7 ═ CH3, R8 ═ R10 ═ CH3)
In a 500mL dry three-necked flask, compound 6(15.4g, 0.1mol) is firstly added and dissolved in 200mL dry tetrahydrofuran, the flask is placed at-10 ℃, compound 7(18.5g, 0.1mol) and t-BuLi (60mL, 1M in THF, 60mmol) are slowly added, the reaction is carried out for 20h under nitrogen atmosphere, water is added after the reaction is finished, the reaction is quenched, then the reaction is extracted by ethyl acetate and water, dried by anhydrous sodium sulfate, concentrated under reduced pressure, and then column chromatography is carried out, so as to obtain compound 8(20g, 77.5%).
Example 3: preparation of compound 2(R5 ═ R7 ═ t-Bu, R8 ═ R10 ═ t-Bu)
In a 500mL dry three-necked flask, compound 9(23.8g, 0.1mol) is firstly added and dissolved in 200mL dry tetrahydrofuran, the flask is placed at-10 ℃, compound 10(26.9g, 0.1mol) and t-BuLi (60mL, 1M in THF, 60mmol) are slowly added, the reaction is carried out for 20h under nitrogen atmosphere, water is added after the reaction is finished, the reaction is quenched, then the reaction is extracted by ethyl acetate and water, dried by anhydrous sodium sulfate, concentrated under reduced pressure, and then column chromatography is carried out, thus obtaining compound 8(21g, 50%).
Compounds for the other groups in Compound 2 were synthesized according to this method.
Example 4: preparation of ligand L6
A50 mL round-bottom flask was charged with Compound 5(1g, 2mmol), Compound 8(620mg, 2.4mmol), CuI (6.48mg, 33.9mmol), Na2CO33.2mL (509mg, 4.8mmol) of acetone was reacted at room temperature for 6 hours, after completion of the reaction, the reaction was extracted with ethyl acetate and water, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and subjected to column chromatography to give ligand L6(0.8g, 63.8%).
Nuclear magnetic data for ligand L6 are as follows:
1H NMR(400MHz,CDCl3)δ7.81,7.80,7.72,7.59,7.17,7.13,6.74,6.70,6.43,6.10,3.70,2.36.
13C NMR(100MHz,CDCl3)δ161.49,159.46,154.08,148.74,147.74,147.67,141.39,139.96,134.29,134.01,132.88,131.69,116.49,116.44,111.83,111.64,71.95,56.08,21.83.
example 5: preparation of ligand L8
A50 mL round-bottom flask was charged with Compound 5(1g, 2mmol), Compound 11(1.02g, 2.4mmol), CuI (0.8mg, 4.2mmol), Na2CO3(932mg, 8.8mmol) of acetone 4mL, at room temperature for 6h, after the reaction, the reaction was extracted with ethyl acetate and water, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and subjected to column chromatography to obtain ligand L8(0.91g, 56.9%).
Nuclear magnetic data for ligand L8 are as follows:
1H NMR(400MHz,CDCl3)δ7.84,7.81,7.80,7.70,7.17,7.13,6.74,6.70,6.43,6.13,3.70,1.32.
13C NMR(100MHz,CDCl3)δ161.49,159.46,154.08,151.35,148.74,147.74,147.67,141.39,134.41,134.29,126.73,126.07,116.49,116.44,111.83,111.64,71.95,56.08,35.51,31.36.
the synthesis of ligands L1-L5, L7, L9 was as described above.
Example 6
In a dry 1L three-necked flask, isooctylaldehyde (160g, 1.25mol) and the solvent 2-ethylhexanoic acid (160g, 1.11mol), ligand L6(5.01mg, 0.008mmol), cesium carbonate (13.03mg, 0.04mmol), potassium acetate 320mg were added, placed in a water bath, mechanically stirred under nitrogen atmosphere, after the temperature had risen to 30 ℃ air was started to be blown in at a flow rate of 11.9g/h, the reaction temperature was maintained at 30-35 ℃ by adding cooling water to the water bath, after 8h of reaction, the conversion of isooctylaldehyde was calculated to be 99.1%, the selectivity of 2-ethylhexanoic acid was calculated to be 99.4%, and the yield was calculated to be 98.50%.
Example 7
In a dry 1L three-necked flask, isooctylaldehyde (80g, 0.62mol) and the solvent 2-ethylhexanoic acid (240g, 1.66mol), ligand L8(5.24mg, 0.007mmol), cesium carbonate (18.24mg, 0.056mmol), potassium acetate 160mg were added, placed in a water bath, mechanically stirred under nitrogen atmosphere, after the temperature had risen to 30 ℃, air was started to flow at a flow rate of 11.9g/h, the reaction temperature was maintained at 30-35 ℃ by adding cooling water to the water bath, after 6h of reaction, the conversion of isooctylaldehyde was 99.6%, the selectivity of 2-ethylhexanoic acid was 99.5%, and the yield was 99.10% as calculated.
Example 8
In a dry 1L three-necked flask, isooctylaldehyde (160g, 1.25mol) and the solvent 2-ethylhexanoic acid (160g, 1.11mol), ligand L8(6.36mg, 0.008mmol), cesium carbonate (13.03mg, 0.040mmol), potassium acetate 0.8g were charged, placed in a water bath, mechanically stirred under nitrogen atmosphere, after the temperature had risen to 30 ℃, air was started to be blown in at a flow rate of 11.9g/h, the reaction temperature was maintained at 30-35 ℃ by adding cooling water to the water bath, and after 6 hours of reaction, the conversion of isooctylaldehyde was 99.6%, the selectivity of 2-ethylhexanoic acid was 99.5%, and the yield was 99.10% as calculated.
Example 9
In a dry 1L three-necked flask, isooctylaldehyde (80g, 0.62mol) and the solvent 2-ethylhexanoic acid (240g, 1.66mol), ligand L6(4.82mg, 0.007mmol), cesium carbonate (18.24mg, 0.056mmol), potassium acetate (0.4 g) were added, placed in a water bath, mechanically stirred under nitrogen, after the temperature had risen to 30 ℃, air was started to be blown in at a flow rate of 11.9g/h, the reaction temperature was maintained at 30-35 ℃ by adding cooling water to the water bath, and after 6h of reaction, the conversion of isooctylaldehyde was 99.7%, the selectivity of 2-ethylhexanoic acid was 99.2%, and the yield was 98.90% were calculated.
Example 10
In a dry 1L three-necked flask, isooctylaldehyde (80g, 0.62mol) and the solvents 2-ethylhexanoic acid (240g, 1.66mol), ligand L1(3.96mg, 0.007mmol), cesium carbonate (11.40mg, 0.035mmol), potassium acetate 80mg were added, placed in a water bath, mechanically stirred under nitrogen atmosphere, after the temperature rose to 30 ℃ air was started to pass through at a flow rate of 11.9g/h, the reaction temperature was maintained at 30-35 ℃ by adding cooling water to the water bath, after 6h of reaction, the conversion of isooctylaldehyde was calculated to be 99.0%, the selectivity of 2-ethylhexanoic acid was calculated to be 98.5%, and the yield was calculated to be 97.51%.
Example 11
In a dry 1L three-necked flask, isooctylaldehyde (80g, 0.62mol) and the solvent 2-ethylhexanoic acid (240g, 1.66mol), ligand L3(4.59mg, 0.008mmol), cesium carbonate (13.03mg, 0.04mmol), potassium acetate (0.48 g) were charged, placed in a water bath, mechanically stirred under nitrogen atmosphere, after the temperature had risen to 30 ℃, air was started to be blown in at a flow rate of 11.9g/h, the reaction temperature was maintained at 30-35 ℃ by adding cooling water to the water bath, and after 6h of reaction, the conversion of isooctylaldehyde was 99.1%, the selectivity of 2-ethylhexanoic acid was 98.2%, and the yield was 97.31% were calculated.
Example 12
In a dry 1L three-necked flask, isooctylaldehyde (80g, 0.62mol) and the solvents 2-ethylhexanoic acid (240g, 1.66mol), ligand L9(3.96mg, 0.007mmol), cesium carbonate (11.40mg, 0.035mmol), potassium acetate 80mg were added, placed in a water bath, mechanically stirred under nitrogen atmosphere, after the temperature rose to 30 ℃ air was started to pass through at a flow rate of 11.9g/h, the reaction temperature was maintained at 30-35 ℃ by adding cooling water to the water bath, after 6h of reaction, the conversion of isooctylaldehyde was calculated to be 98.8%, the selectivity of 2-ethylhexanoic acid to be 98.3%, and the yield to be 97.12%.
Claims (20)
1. An iodophosphine oxide ligand of the general formula:
wherein R is11、R12Each independently represents a group selected from CF3F, Br or selected from CH3、OCH3、C(CH3)3Electron donating functional groups in (1).
2. The iodophosphine oxide ligand of claim 1, which is one or more of L1-L4, L6-L9, L1-L4, L6-L9 have the following structural formula:
3. a process for the preparation of an iodophosphine oxy ligand as defined in claim 1 or claim 2, comprising the steps of:
reacting compound 1 and compound 2 in CuI and Na2CO3Synthesizing an iodophosphine oxide ligand under the action of acetone:
the structural formulas of compound 1 and compound 2 are as follows:
wherein R11-R12 each independently represent a group selected from CF3F, Br or selected from CH3、OCH3、C(CH3)3Electron donating functional groups in (1).
4. The method according to claim 3, wherein the molar ratio of compound 1 to compound 2 is 1:0.5 to 1.5.
5. The method according to claim 4, wherein the molar ratio of Compound 1 to Compound 2 is 1:0.8 to 1.2.
6. The production method according to any one of claims 3 to 5, wherein CuI is added in an amount of 0.1 to 0.6 wt% based on the total amount of Compound 1 and Compound 2; and/or
Na2CO3The ratio of the added molar amount of the compound (2) to the total molar amount of the compound (1) and the compound (2) is 1:1-4: 1; and/or
The ratio of the volume of acetone added V/mL to the total mass of compound 1 and compound 2 is 1.5:1-4: 1.
7. The production method according to any one of claims 3 to 5, wherein CuI is added in an amount of 0.2 to 0.4 wt% based on the total amount of Compound 1 and Compound 2; and/or
Na2CO3The ratio of the added molar quantity of the compound (1) to the total molar quantity of the compound (2) is 1:1-2: 1; and/or
The ratio of the volume of acetone added V/mL to the total mass of compound 1 and compound 2 is 1.5:1-2: 1.
8. The production method according to any one of claims 3 to 5, wherein the reaction is carried out at normal temperature and normal pressure for 6 to 12 hours.
9. A complex of the iodophosphinyl oxygen ligand of claim 1 or 2 with cesium.
10. A catalyst system comprising a catalyst and a promoter, wherein the promoter is a potassium salt and the catalyst is a complex of an iodophosphine oxide ligand of claim 9 with cesium.
11. The catalyst system of claim 10, wherein the potassium salt is selected from one or more of potassium nitrate, potassium carbonate, potassium chloride, potassium sulfate, potassium bisulfate, potassium phosphate, potassium iodide, potassium acetate, potassium bromide, potassium fluoride.
12. The catalyst system of claim 10 or 11, wherein the cesium source is one or more of cesium carbonate, cesium hydroxide, cesium acetate, cesium nitrate.
13. The catalyst system of claim 10 or 11, wherein the molar ratio of cesium to iodophosphine oxide ligand in the catalyst is from 1:1 to 10: 1.
14. The catalyst system of claim 10 or 11, wherein the molar ratio of cesium to iodophosphine oxide ligand in the catalyst is from 5:1 to 8: 1.
15. A method for preparing isooctanoic acid by the oxidation of isooctanal, comprising: oxidizing isooctanal in the presence of a catalyst system according to any of claims 10 to 14 in an atmosphere comprising oxygen to give isooctanoic acid.
16. The method according to claim 15, wherein iso-octanal (2-ethylhexanal) is mixed with a solvent to serve as a reaction raw material, the mass fraction of 2-ethylhexanal in the reaction raw material is 25-50 wt%, and the solvent is n-octanoic acid or 2-ethylhexanoic acid, or a mixed solvent of the n-octanoic acid and the 2-ethylhexanoic acid in any ratio.
17. The process of claim 16, wherein the mass fraction of 2-ethylhexanal in the reaction feed is 35-45 wt%, and the solvent is 2-ethylhexanoic acid.
18. The method as claimed in any one of claims 15 to 17, wherein the mass fraction of the iodophosphinyl oxygen ligand and cesium complex catalyst in the reaction raw material 2-ethylhexanal is 100-600 ppm; the mass percentage range of the potassium salt of the cocatalyst accounting for the usage of the reaction raw material 2-ethylhexanal is 0.1-0.6 wt%.
19. The process as claimed in any one of claims 15 to 17, wherein the mass fraction of the iodophosphinyl oxygen ligand and cesium complex catalyst in the reaction raw material 2-ethylhexanal is 100-500 ppm; the mass percentage range of the potassium salt of the cocatalyst accounting for the usage of the reaction raw material 2-ethylhexanal is 0.2-0.5 wt%.
20. Use of the catalyst system according to any one of claims 10 to 14 as a catalyst for the oxidation of isooctylaldehyde to produce isooctanoic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811112669.4A CN109134538B (en) | 2018-09-25 | 2018-09-25 | Iodophosphine oxide ligands, method for the production thereof, complexes, catalyst systems comprising the complexes and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811112669.4A CN109134538B (en) | 2018-09-25 | 2018-09-25 | Iodophosphine oxide ligands, method for the production thereof, complexes, catalyst systems comprising the complexes and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109134538A CN109134538A (en) | 2019-01-04 |
| CN109134538B true CN109134538B (en) | 2021-05-14 |
Family
ID=64823388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811112669.4A Active CN109134538B (en) | 2018-09-25 | 2018-09-25 | Iodophosphine oxide ligands, method for the production thereof, complexes, catalyst systems comprising the complexes and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109134538B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110776412B (en) * | 2019-11-12 | 2022-04-22 | 万华化学集团股份有限公司 | Method for preparing isovaleric acid, ligand, complex and application thereof in catalytic system |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53105413A (en) * | 1977-02-28 | 1978-09-13 | Mitsubishi Chem Ind Ltd | Preparation of alpha-branched aliphatic carboxylic acid |
| CN1422840A (en) * | 2001-11-29 | 2003-06-11 | 中国石化集团齐鲁石油化工公司 | 2-ethyl hexanoic acid production method |
| CN103087105A (en) * | 2013-01-18 | 2013-05-08 | 中国科学院上海有机化学研究所 | Chiral phosphine ligand and metal catalyst comprising same and application of chiral phosphine ligand and metal catalyst |
| CN104945238A (en) * | 2015-06-03 | 2015-09-30 | 郸城县凯杰科技有限公司 | Isocaprylic acid production process |
| CN105263942A (en) * | 2013-11-19 | 2016-01-20 | 株式会社Lg化学 | Ligand compound, catalyst system for oligomerizing olefin, and method for oligomerizing olefin using same |
| CN108238892A (en) * | 2017-04-05 | 2018-07-03 | 成都东电艾尔科技有限公司 | A kind of synthetic method of pharmaceutical intermediate 2 ethyl hexanoic acid |
| CN108250069A (en) * | 2018-01-22 | 2018-07-06 | 万华化学集团股份有限公司 | A kind of preparation method of isooctyl acid |
| CN108503530A (en) * | 2017-02-28 | 2018-09-07 | 中国石油化工股份有限公司 | A kind of process preparing isooctyl acid |
-
2018
- 2018-09-25 CN CN201811112669.4A patent/CN109134538B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53105413A (en) * | 1977-02-28 | 1978-09-13 | Mitsubishi Chem Ind Ltd | Preparation of alpha-branched aliphatic carboxylic acid |
| CN1422840A (en) * | 2001-11-29 | 2003-06-11 | 中国石化集团齐鲁石油化工公司 | 2-ethyl hexanoic acid production method |
| CN103087105A (en) * | 2013-01-18 | 2013-05-08 | 中国科学院上海有机化学研究所 | Chiral phosphine ligand and metal catalyst comprising same and application of chiral phosphine ligand and metal catalyst |
| CN105263942A (en) * | 2013-11-19 | 2016-01-20 | 株式会社Lg化学 | Ligand compound, catalyst system for oligomerizing olefin, and method for oligomerizing olefin using same |
| CN104945238A (en) * | 2015-06-03 | 2015-09-30 | 郸城县凯杰科技有限公司 | Isocaprylic acid production process |
| CN108503530A (en) * | 2017-02-28 | 2018-09-07 | 中国石油化工股份有限公司 | A kind of process preparing isooctyl acid |
| CN108238892A (en) * | 2017-04-05 | 2018-07-03 | 成都东电艾尔科技有限公司 | A kind of synthetic method of pharmaceutical intermediate 2 ethyl hexanoic acid |
| CN108250069A (en) * | 2018-01-22 | 2018-07-06 | 万华化学集团股份有限公司 | A kind of preparation method of isooctyl acid |
Non-Patent Citations (1)
| Title |
|---|
| "醛氧化法合成异辛酸工艺的研究进展";刁香等;《精细石油化工进展》;20010430;第2卷(第4期);第37-39页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109134538A (en) | 2019-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | An ionic liquid as a recyclable medium for the green preparation of α, α′-bis (substituted benzylidene) cycloalkanones catalyzed by FeCl 3· 6H 2 O | |
| CN108250069B (en) | Preparation method of isooctanoic acid | |
| CN108707076A (en) | A kind of preparation method of 4- acetoxyl-2-methyl-2-butylenoic aldehydes | |
| CN104193600A (en) | Method for preparing aldehyde or ketone from air oxidized alcohol by using aluminum oxide as co-catalyst | |
| CN114716371B (en) | N-containing active center metal organic catalyst for synthesizing cyclic carbonate, and preparation method and application thereof | |
| CN106866326A (en) | A kind of method that primary alconol prepares nitrile | |
| CN109134538B (en) | Iodophosphine oxide ligands, method for the production thereof, complexes, catalyst systems comprising the complexes and use thereof | |
| CN101830783B (en) | Method for preparing aldehyde by oxidizing alcohol with oxygen in presence of Schiff-base complex catalyst | |
| CN109776488B (en) | Synthesis method of alpha-ketoamide compound with ortho-aldehyde group | |
| CN106588738B (en) | The synthetic method of N-Boc-3- pyrrolidine formaldehyde | |
| CN108059593B (en) | Method for preparing organic acid by oxidative cracking of aromatic secondary alcohol | |
| CN106349163B (en) | One kind being based on the metal organic coordination polymer and the preparation method and application thereof of Cu (I) | |
| CN102942548B (en) | Delta-dodecalactone synthesis method | |
| CN103755526A (en) | Method of preparing alpha-phenethyl alcohol compounds by catalytic oxidation of side chains of aromatic hydrocarbon by using metalloporphyrin | |
| CN104926888A (en) | Cobalt complex and preparation method and application thereof | |
| CN109438402B (en) | Benzofuranone derivatives and synthesis method thereof | |
| CN113548965A (en) | Preparation method of 1, 4-eneyne compound | |
| CN106187730A (en) | A kind of 4 propioloyl benzaldehydes and preparation method thereof | |
| CN115947705B (en) | Method for preparing 1-nitrodibenzofuran by using ligand and o-bromophenol as raw materials | |
| CN114736239B (en) | Bidentate phosphine ligand, and preparation method and application thereof | |
| CN115215762B (en) | Method for synthesizing aliphatic nitrile from alcohol | |
| CN115093346B (en) | Method for preparing nitrile compound from different substituted cycloalkanone in one step | |
| CN115160115B (en) | Method for preparing acetone by biomimetic catalysis of isobutene | |
| CN113548958B (en) | Preparation method of adipic acid | |
| CN112479843B (en) | Preparation method of 5-methyl-3-cyclohexenone and application thereof in preparation of m-cresol |
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 |