CN114456041A - Preparation method of isomeric tridecanol - Google Patents

Preparation method of isomeric tridecanol Download PDF

Info

Publication number
CN114456041A
CN114456041A CN202210154982.4A CN202210154982A CN114456041A CN 114456041 A CN114456041 A CN 114456041A CN 202210154982 A CN202210154982 A CN 202210154982A CN 114456041 A CN114456041 A CN 114456041A
Authority
CN
China
Prior art keywords
phase
rhodium
preparing
reaction
isotridecanol
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.)
Pending
Application number
CN202210154982.4A
Other languages
Chinese (zh)
Inventor
李燕平
陈子涛
庞海舰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong Renkangda Material Technology Co ltd
Original Assignee
Guangdong Renkangda Material Technology Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Guangdong Renkangda Material Technology Co ltd filed Critical Guangdong Renkangda Material Technology Co ltd
Priority to CN202210154982.4A priority Critical patent/CN114456041A/en
Publication of CN114456041A publication Critical patent/CN114456041A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • 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
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1865—Phosphonites (RP(OR)2), their isomeric phosphinates (R2(RO)P=O) and RO-substitution derivatives thereof
    • 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
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/189—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
    • 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
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2221—At least one oxygen and one phosphorous atom present as complexing atoms in an at least bidentate or bridging ligand
    • 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
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C07C45/505—Asymmetric hydroformylation
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium

Abstract

The invention relates to the technical field of C07F9/50, and in particular relates to a preparation method of isomeric tridecanol, which comprises the following steps: the isododecene is prepared through hydroformylation in a liquid-liquid two-phase catalytic system comprising ionic liquid phase and organic solvent phase, and subsequent extraction and hydrogenation. The method uses a liquid-liquid two-phase reaction system, the reaction process is simple and efficient, the catalyst is good in stability and effect in recycling, and the method is suitable for preparing high-carbon alcohols such as isotridecanol and has a good industrial prospect.

Description

Preparation method of isomeric tridecanol
Technical Field
The invention relates to the technical field of C07F9/50, and in particular relates to a preparation method of isomeric tridecanol.
Background
The isomeric tridecanol is used as a special isomeric alcohol, and the application of the isomeric tridecanol is mainly to synthesize isomeric alcohol polyoxyethylene ether by reacting with ethylene oxide, and the isomeric alcohol polyoxyethylene ether is used as a special surfactant product. As the product has the characteristics of extremely low pour point, no gel at high concentration, excellent wettability, degreasing and oil removal capability and the like, the product is a new green surface variety and is an ideal product for replacing alkylphenol ether. Has wide application in the field of textile auxiliary agents, and has very good application prospect in the field of daily chemicals, particularly ultra-concentrated laundry detergent, metal processing and industrial cleaning. At present, isomeric tridecanol products cannot be obtained from a natural oil hydrogenation process, and are industrially prepared by a high-pressure hydroformylation process. However, the high-pressure method has large investment and high process risk, while the low-pressure rhodium process developed by the Kingfei Daiwei has great success in the field of hydroformylation of short-carbon-chain olefins, particularly butanol and octanol, but cannot solve the problems of separation and inactivation of homogeneous rhodium in the field of hydroformylation of long-carbon-chain olefins, so that the rhodium catalyst cannot be applied to the industrial field of hydroformylation of high-carbon-chain olefins on a large scale.
Disclosure of Invention
In view of the problems of the prior art, the first aspect of the present invention provides a method for preparing isomeric tridecanols, comprising: the isododecene is prepared through hydroformylation in a liquid-liquid two-phase catalytic system comprising ionic liquid phase and organic solvent phase, and subsequent extraction and hydrogenation.
In one embodiment, the ionic liquid phase comprises an ionic liquid, an organophosphine ligand comprising an imidazolium salt, a rhodium catalyst.
The ionic liquid described herein includes, but is not limited to, ionic liquids such as imidazoles, pyridines, piperidines, guanidine salts, and quaternary ammonium salts, and specific examples thereof include 1-hexyl-3-methylimidazolium hexafluorophosphate, N-octylpyridine bromide, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-dodecyl-3-methylimidazolium bromide, and N-hexylpyridine hexafluorophosphate.
In one embodiment, the organophosphine ligand comprising an imidazolium salt has the structure of formula (1) or formula (2);
Figure BDA0003512101950000021
wherein R is1，R2，R3，R4Are each independently C1-12An alkyl group or an alkoxy group.
In this application C1-12Examples of the alkyl group include methyl, ethyl, propyl, butyl, isopropyl, and isobutyl.
Examples of the alkoxy group in the present application include a methoxy group and an ethoxy group.
In one embodiment, the organophosphine ligand comprising an imidazolium salt includes, but is not limited to, the following structure:
Figure BDA0003512101950000022
and the like.
The organophosphine ligands containing imidazolium salts in the present application are either commercially available or can be prepared by methods routinely selected by those skilled in the art.
The preparation method of the organic phosphine ligand L1 is as follows:
2.8g of 1-butyl-3-methylimidazolium hexafluorophosphate [ BMIM ] was added to a three-necked flask under protection of Ar gas]PF6 -And 60mL of redistilled anhydrous dichloromethane, and after cooling to-78 deg.C, 5.5mL of LDA in n-hexane (2M) was slowly added to the flask. After the reaction is kept warm for 1h, 4.2g of the prepared diphenol-based phosphorus chloride dichloromethane solution (50mL) is slowly added dropwise, the reaction is kept warm for 1h after the dropwise addition is finished, and then the reaction is slowly raised to room temperature for continuous reaction for 6 h. After the reaction is finished, adding 30mL of pure water for quenching, then carrying out phase separation, extracting the upper-layer water phase twice by using 30mL of anhydrous dichloromethane, combining organic phases, drying, concentrating to obtain yellow oily matter, adding a small amount of n-hexane, stirring, precipitating solid, filtering, and recrystallizing the solid by using a mixed solvent of ethyl acetate and n-hexane again to obtain white phosphine ligand L13.5 g containing the imidazolium salt, wherein the yield is about 53%. Involving a reaction of
Figure BDA0003512101950000031
The preparation method of the organic phosphine ligand L3 is as follows:
3.6g of 1,1 '-propyl-3, 3' -ethylbisimidazole hexafluorophosphate and 60mL of redistilled anhydrous dichloromethane were added to a three-necked flask under protection of Ar gas, cooled to-78 ℃, and after cooling, 11mL of LDA in n-hexane (2M) was slowly added to the flask. After the reaction is kept warm for 1h, 8.4g of the prepared diphenol-based phosphorus chloride dichloromethane solution (70mL) is slowly added dropwise, the reaction is kept warm for 1h after the dropwise addition is finished, and then the reaction is slowly raised to room temperature for continuous reaction for 6 h. After the reaction is finished, adding 50mL of pure water for quenching, then carrying out phase separation, extracting the upper aqueous phase twice by using 40mL of anhydrous dichloromethane, combining organic phases, drying, concentrating to obtain yellow oily matter, adding a small amount of normal hexane, stirring, and separating out solidAfter filtration, the solid was recrystallized from a mixed solvent of ethyl acetate and n-hexane again to obtain 34.9 g of a white phosphine ligand containing an imidazolium salt with a yield of about 44%. Involving a reaction of
Figure BDA0003512101950000032
In one embodiment, the rhodium catalyst includes, but is not limited to, rhodium chloride, rhodium acetate, rhodium acetylacetonate dicarbonyl, cyclooctadiene rhodium, rhodium octanoate dimer, and the like.
In one embodiment, the organic solvent is C6-12An alkane solvent.
In this application C6-12Examples of the alkane solvent include hexane, cyclohexane, methylcyclohexane, heptane, octane, nonane, decane, and dodecane.
In one embodiment, the ionic liquid and organic solvent are added in an amount of (60-80) g: 45mL, preferably 70 g: 45 mL.
In one embodiment, the volume ratio of the organic solvent to isododecene is (1-10): 1, preferably 1.3: 1.
In one embodiment, the isododecene and rhodium catalyst has a mass ratio of (100-: 1.
in one embodiment, the weight ratio of the organophosphine ligand to the rhodium catalyst is (1-10) g: (30-200) mg.
In one embodiment, the method for preparing isomeric tridecanols comprises: in a liquid-liquid two-phase catalytic system consisting of an ionic liquid phase and an organic solvent phase, the pressure of the reaction synthesis gas is controlled to be 1-20MPa, and the synthesis gas H2Volume ratio to CO 1: (0.1-10) and the reaction temperature is 80-200 ℃, the hydroformylation reaction is carried out for 1-20h, then the ionic liquid phase containing the catalyst is separated from the hydroformylation product after phase separation and extraction, and the hydroformylation product is obtained by distillation after hydrogenation.
In the application, the lower layer ionic liquid containing the catalyst can be continuously recycled after being separated from the product.
In a preferred embodiment, the isomeric tridecanols are preparedThe method comprises the following steps: in a liquid-liquid two-phase catalytic system consisting of an ionic liquid phase and an organic solvent phase, the pressure of the reaction synthesis gas is controlled to be 4-5MPa, and the synthesis gas H2Volume ratio to CO 1:1, performing hydroformylation reaction for 6 hours at the reaction temperature of 120 ℃, separating and extracting an ionic liquid phase containing a catalyst from a hydroformylation product, and distilling the hydroformylation product after the hydrogenation reaction to obtain the catalyst.
Preferably, the hydroformylation product hydrogenation reaction temperature is 80-200 ℃, more preferably 105 ℃.
Preferably, the pressure of the hydroformylation product hydrogenation reaction is in the range of from 1 to 10MPa, more preferably 3 MPa.
Preferably, the hydroformylation product is hydrogenated for a period of from 1 to 24 hours, more preferably for 3 hours.
The hydrogenation catalyst used in the hydroformylation product hydrogenation process can be selected conventionally in the art, for example, metal catalysts such as nickel, palladium, ruthenium, copper, etc., and the content thereof can be selected conventionally by those skilled in the art.
In the prior art, isomeric tridecanols are obtained by hydroformylation of isododecene followed by hydrogenation, according to the structure of isododecene as follows:
Figure BDA0003512101950000041
Figure BDA0003512101950000042
as a long-carbon alkene, the carbon chain structure not only has terminal olefin, but also has partial internal olefin, the catalytic hydroformylation reaction is difficult, and the industry is mainly based on a high-pressure method for a long time. Due to the high boiling point of the hydroformylation product, the deactivation phenomenon is easy to occur when the rhodium catalyst is separated, so that the industrial problem that the rhodium catalyst cannot be recycled for a long time is caused. The method adopts a liquid-liquid two-phase system, greatly reduces the reaction pressure, can realize reaction under the condition of medium and low pressure, realizes repeated recycling of the catalyst, avoids the phenomenon of high-temperature inactivation of the catalyst, can effectively catalyze the hydroformylation reaction of the isododecene, and has good industrialization prospect.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method uses a liquid-liquid two-phase reaction system, the reaction process is simple and efficient, the catalyst is good in stability and effect in recycling, and the method is suitable for preparing high-carbon alcohols such as isotridecanol and has a good industrial prospect;
(2) the method uses a liquid-liquid two-phase reaction system, can carry out reaction under low pressure, solves the high-pressure reaction condition in the prior art, and avoids the problems of catalyst inactivation and difficult circulation;
(3) the method adopts a liquid-liquid two-phase reaction system, and uses organic phosphine ligands L3 and/or L4, so that the content of the isomeric tridecanal in the obtained intermediate product is high and is higher than 60%;
(4) in the application, a system obtained by the ionic liquid of the 1-octyl-3-methylimidazolium hexafluorophosphate and/or the 1-dodecyl-3-methylimidazolium bromide and the rhodium chloride catalyst has high catalytic efficiency, and the content of isomeric tridecanal is further improved to be higher than 65%;
(5) the ionic liquid phase formed by the ligand L3, the 1-octyl-3-methylimidazole hexafluorophosphate and the rhodium trichloride has better cyclic usability, and the conversion rate of olefin and the content of products are not reduced basically.
Drawings
FIG. 1 is a gas chromatogram of the product of example 1 of the present application.
Detailed Description
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
Examples
Example 1
70g of 1-butyl-3-methylimidazolium hexafluorophosphate, 45mL of n-heptane, 35mL of isododecene, 12.1 g of phosphine ligand L and Rh (CO) were added to a 250mL autoclave2after acac 40mg, the autoclave was purged with Ar three times, followed by evacuation and introduction of synthesis gas (CO: H)21:1 by volume) to 4MPa, stirring was started and the temperature was raised. The temperature in the kettle rises to 120 ℃, the pressure is 5.5MPa, the reaction starts, and the reaction pressure is controlledThe reaction is maintained at 5MPa for 6 h. After the reaction is finished, cooling to room temperature, decompressing to normal pressure and opening the kettle. And (3) carrying out phase separation on the reaction liquid in the kettle, separating out an upper organic phase, and extracting a lower ionic liquid phase twice by using 50mL of n-heptane. And combining the upper organic phases to obtain a reaction liquid containing the isomeric tridecanol. After removal of the solvent, the isomeric tridecanal content was analyzed by gas chromatography (see FIG. 1) to give 47%.
Example 2
After 70g of 1-hexyl-3-methylimidazolium hexafluorophosphate, 45mL of methylcyclohexane, 35mL of isododecene, 24.4 g of phosphine ligand and 125mg of rhodium octanoate were added to a 250mL autoclave, the autoclave was purged with Ar three times, followed by evacuation and introduction of synthesis gas (CO: H)21:1 by volume) to 4MPa, stirring was started and the temperature was raised. The temperature in the kettle is raised to 120 ℃, the pressure is 5.5MPa, the reaction starts, the reaction pressure is controlled to be maintained at 5MPa, and the reaction time is 6 hours. After the reaction is finished, cooling to room temperature, decompressing to normal pressure and opening the kettle. And (3) carrying out phase separation on the reaction liquid in the kettle, separating an upper organic phase, and extracting a lower ionic liquid phase twice by using 50mL of methylcyclohexane. And combining the upper organic phases to obtain a reaction liquid containing the isomeric tridecanol. After the solvent was removed, the isomeric tridecanal content was analyzed by gas chromatography at 52%.
Example 3
After 70g of 1-hexyl-3-methylimidazolium hexafluorophosphate, 45mL of dodecane, 35mL of isododecene, 35.6 g of phosphine ligand L35 and 40mg of rhodium acetylacetonate dicarbonyl were added to a 250mL autoclave respectively, the autoclave was purged with Ar three times and then evacuated, and then, synthesis gas (CO: H) was introduced21:1 by volume) to 4MPa, stirring was started and the temperature was raised. The temperature in the kettle is raised to 120 ℃, the pressure is 5.5MPa, the reaction starts, the reaction pressure is controlled to be maintained at 5MPa, and the reaction time is 6 hours. After the reaction is finished, cooling to room temperature, decompressing to normal pressure and opening the kettle. And (3) carrying out phase separation on the reaction liquid in the kettle, separating out an upper organic phase, and extracting a lower ionic liquid phase twice by 50mL of dodecane respectively. And combining the upper organic phases to obtain a reaction liquid containing the isomeric tridecanol. After removal of the solvent, the isomeric tridecanal content was analyzed by gas chromatography to 67%.
Example 4
70g N-octylpyridinium bromide, 45mL of dodecane, 35mL of isododecene, 49.1g of phosphine ligand and 35mg of rhodium trichloride were added to a 250mL autoclave, and then the autoclave was purged with Ar three times and then evacuated, and then, a synthetic gas (CO: H) was introduced21:1 by volume) to 4MPa, stirring was started and the temperature was raised. The temperature in the kettle is raised to 120 ℃, the pressure is 5.5MPa, the reaction starts, the reaction pressure is controlled to be maintained at 5MPa, and the reaction time is 6 hours. After the reaction is finished, cooling to room temperature, decompressing to normal pressure and opening the kettle. And (3) carrying out phase separation on the reaction liquid in the kettle, separating out an upper organic phase, and extracting a lower ionic liquid phase twice by 50mL of dodecane respectively. And combining the upper organic phases to obtain a reaction liquid containing the isomeric tridecanol. After removal of the solvent, the isomeric tridecanal content was 61% by gas chromatography.
Example 5
6g of Raney nickel catalyst is added into the upper organic phase which is amplified by 8 times and combined in the hydroformylation reaction of the embodiment 3, hydrogen is replaced in a reaction kettle, the reaction temperature is 105 ℃, the reaction pressure is controlled to be 3MPa, the reaction is finished after 3 hours, the pressure is released out of the kettle after the reaction is finished, the reaction liquid is distilled after the solvent is removed, 162g of isomeric tridecanol can be obtained, the yield is 64 percent by gas chromatography, and the purity is 99 percent.
Example 6
The preparation method steps are the same as example 3, except that 1-hexyl-3-methylimidazolium hexafluorophosphate is replaced by 1-ethyl-3-methylimidazolium hexafluorophosphate, rhodium acetylacetonate dicarbonyl is replaced by rhodium trichloride, and the molar ratio of the organophosphine ligand to the rhodium catalyst is kept constant.
Example 7
The preparation method steps are the same as example 3, except that 1-hexyl-3-methylimidazolium hexafluorophosphate is replaced by 1-butyl-3-methylimidazolium hexafluorophosphate, rhodium acetylacetonate dicarbonyl is replaced by rhodium trichloride, and the molar ratio of the organophosphine ligand to the rhodium catalyst is kept constant.
Example 8
The procedure is as in example 3 except that rhodium acetylacetonate dicarbonyl is replaced with rhodium trichloride and the molar ratio of the organophosphine ligand to the rhodium catalyst is maintained.
Example 9
The preparation method steps are the same as example 3, except that 1-hexyl-3-methylimidazolium hexafluorophosphate is replaced by 1-octyl-3-methylimidazolium hexafluorophosphate, rhodium acetylacetonate dicarbonyl is replaced by rhodium trichloride, and the molar ratio of the organic phosphine ligand to the rhodium catalyst is kept constant.
Example 10
The preparation method steps are the same as example 3, except that 1-hexyl-3-methylimidazolium hexafluorophosphate is replaced by 1-dodecyl-3-methylimidazolium bromide, rhodium acetylacetonate dicarbonyl is replaced by rhodium trichloride, and the molar ratio of the organophosphine ligand to the rhodium catalyst is kept constant.
Example 11
The preparation method steps are the same as example 3, except that 1-hexyl-3-methylimidazolium hexafluorophosphate is replaced by N-hexylpyridine hexafluorophosphate, rhodium acetylacetonate dicarbonyl is replaced by rhodium trichloride, and the molar ratio of the organic phosphine ligand to the rhodium catalyst is kept constant.
The reaction products of examples 6-11 were analyzed by gas chromatography and represented the following Table 1.
TABLE 1
Figure BDA0003512101950000071
Figure BDA0003512101950000081
The lower ionic liquid phase of example 9 was reused after extraction with dodecane, and the content of each substance in the product was analyzed by gas chromatography after each reuse to calculate the conversion of isododecene and the content of isomeric tridecanal, the results of which are shown in table 2.
TABLE 2
Figure BDA0003512101950000082
It can be seen from the results in table 2 that the isododecene conversion and the yield of isomeric tridecanal are stable without significant decrease after multiple recycling.

Claims (10)

1. A method for preparing isomeric tridecanol, which is characterized by comprising the following steps: the isododecene is prepared through hydroformylation in a liquid-liquid two-phase catalytic system comprising ionic liquid phase and organic solvent phase, and subsequent extraction and hydrogenation.
2. The method for preparing isotridecanol according to claim 1, wherein said ionic liquid phase comprises an ionic liquid, an organophosphine ligand containing imidazolium salt, and a rhodium catalyst, wherein the structure of the organophosphine ligand containing imidazolium salt is as shown in formula (1) or formula (2);
Figure FDA0003512101940000011
Figure FDA0003512101940000012
wherein R is1，R2，R3，R4Are each independently C1-12An alkyl group or an alkoxy group.
3. The method for preparing isotridecanol as claimed in claim 2, wherein said organophosphine ligand containing imidazolium salt is selected from the group consisting of
Figure FDA0003512101940000013
Figure FDA0003512101940000014
One or more of them.
4. The method for preparing isotridecanol according to claim 2, wherein said ionic liquid is selected from one or more of imidazoles, pyridines, piperidines, guanidinium salts, and quaternary ammonium salts.
5. The method for preparing isotridecanol according to claim 4, wherein said rhodium catalyst is selected from one or more of rhodium chloride, rhodium acetate, rhodium dicarbonyl acetylacetonate, rhodium cyclooctadiene and rhodium octanoate dimer.
6. The method for preparing isotridecanol as claimed in claim 5, wherein said organic solvent is C6-12An alkane solvent.
7. The method for preparing isomeric tridecanols of any of claims 1-6, wherein said method comprises: in a liquid-liquid two-phase catalytic system consisting of an ionic liquid phase and an organic solvent phase, the pressure of the reaction synthesis gas is controlled to be 1-20MPa, and the synthesis gas H2Volume ratio to CO 1: (0.1-10) and the reaction temperature is 80-200 ℃, the hydroformylation reaction is carried out for 1-20h, then the ionic liquid phase containing the catalyst is separated from the hydroformylation product after phase separation and extraction, and the hydroformylation product is obtained by distillation after hydrogenation.
8. The method for preparing isotridecanol according to claim 7, wherein said ionic liquid and organic solvent are added in an amount of (60-80) g: 45 mL.
9. The method for preparing isotridecanol according to claim 8, wherein the weight ratio of said organophosphine ligand to said rhodium catalyst is (1-10) g: (30-200) mg.
10. The process for preparing isotridecanol as claimed in claim 8 or 9, wherein the hydroformylation product is hydrogenated at a temperature of 80-200 ℃ under a pressure of 1-10MPa for a period of 1-24 hours.
CN202210154982.4A 2022-02-21 2022-02-21 Preparation method of isomeric tridecanol Pending CN114456041A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210154982.4A CN114456041A (en) 2022-02-21 2022-02-21 Preparation method of isomeric tridecanol

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210154982.4A CN114456041A (en) 2022-02-21 2022-02-21 Preparation method of isomeric tridecanol

Publications (1)

Publication Number Publication Date
CN114456041A true CN114456041A (en) 2022-05-10

Family

ID=81416383

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210154982.4A Pending CN114456041A (en) 2022-02-21 2022-02-21 Preparation method of isomeric tridecanol

Country Status (1)

Country Link
CN (1) CN114456041A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1833774A (en) * 2006-04-20 2006-09-20 大连理工大学 Prepn. of high carbon aldehyde by formylating high carbon olefinic hydrogen in temp ion liquid two-phase system
CN102658205A (en) * 2012-04-19 2012-09-12 华东师范大学 Catalyst for producing aldehyde through hydroformylation of alkene and application thereof
CN111718237A (en) * 2020-07-07 2020-09-29 万华化学集团股份有限公司 Preparation method of bio-based isomeric tridecanol
CN111892482A (en) * 2020-06-24 2020-11-06 万华化学集团股份有限公司 Preparation method of isomeric tridecanol
CN112442087A (en) * 2020-11-26 2021-03-05 上海簇睿低碳能源技术有限公司 Preparation method and application of ionic phosphoramidite ligand

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1833774A (en) * 2006-04-20 2006-09-20 大连理工大学 Prepn. of high carbon aldehyde by formylating high carbon olefinic hydrogen in temp ion liquid two-phase system
CN102658205A (en) * 2012-04-19 2012-09-12 华东师范大学 Catalyst for producing aldehyde through hydroformylation of alkene and application thereof
CN111892482A (en) * 2020-06-24 2020-11-06 万华化学集团股份有限公司 Preparation method of isomeric tridecanol
CN111718237A (en) * 2020-07-07 2020-09-29 万华化学集团股份有限公司 Preparation method of bio-based isomeric tridecanol
CN112442087A (en) * 2020-11-26 2021-03-05 上海簇睿低碳能源技术有限公司 Preparation method and application of ionic phosphoramidite ligand

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
林棋等: "离子液体中水溶性催化剂催化长链烯烃氢甲酰化反应", 闽江学院学报, vol. 28, no. 5, pages 88 - 95 *

Similar Documents

Publication Publication Date Title
Doucet et al. trans‐[RuCl2 (phosphane) 2 (1, 2‐diamine)] and Chiral trans‐[RuCl2 (diphosphane)(1, 2‐diamine)]: Shelf‐Stable Precatalysts for the Rapid, Productive, and Stereoselective Hydrogenation of Ketones
CA2422029C (en) Catalytic hydrogenation processes
CN101722048B (en) Catalyst for preparing aldehyde by two-phase catalytic hydrogen formylation reaction and application thereof
CN112608340B (en) Tetradentate nitrogen phosphine ligand, preparation method and application thereof
Sellin et al. Hydroformylation of alkenes in supercritical carbon dioxide catalysed by rhodium trialkylphosphine complexes
Sauvage et al. Imidazol (in) ium‐2‐carboxylates as N‐Heterocyclic Carbene Precursors for the Synthesis of Second Generation Ruthenium Metathesis Catalysts
Gorbunov et al. Hydroformylation in petroleum chemistry and organic synthesis: Implementation of the process and solving the problem of recycling homogeneous catalysts
CN111606792A (en) Method for preparing high-carbon aldehyde
EP0922691B1 (en) Hydroformylation process
EP0924182B1 (en) Process for the preparation of aldehydes
CN114456041A (en) Preparation method of isomeric tridecanol
Lecocq et al. Biphasic Ni-catalyzed ethylene oligomerization in ionic liquids
US4731485A (en) Process for hydroformylation with rhodium catalysts and the separation of rhodium therefrom
CA1257878A (en) Process for the production of nonadecanediols
US6187962B1 (en) Hydroformylation process
JP3712093B2 (en) Method for producing tricyclodecandicarbaldehyde
EP1106595B1 (en) Improved hydroformylation process with cobalt and/or rhodium based catalysts in a biphasic medium
CN1847222A (en) Temperature controlled ionic liquid two-phase system and its application in complexing catalytic hydrogenation
JP2857055B2 (en) Method for producing 1,9-nonandial
US5169981A (en) Synthesis of alpha-substituted alkadienes
CA1215720A (en) PROCESS FOR PRODUCING .alpha.-ACETOXYPROPIONALDEHYDE
EP0151515B1 (en) Hydroformylation of allyl alcohol
Starodubtseva et al. Enantioselective hydrogenation of ethyl 4-chloro-3-oxobutyrate in solutions of organic salts with recycling of the catalyst Ru-BINAP
JP2002516300A (en) Method for hydroformylation of olefins under catalysis in the state of microemulsions
EP2838872B1 (en) Method for producing branched alcohols

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