CN113754615A - Application of one-class bidentate alkyl phosphine ligand in synthesis of fluorescent dye intermediate through olefin hydroformylation - Google Patents
Application of one-class bidentate alkyl phosphine ligand in synthesis of fluorescent dye intermediate through olefin hydroformylation Download PDFInfo
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- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
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- 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
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- 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
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Abstract
The invention discloses an application of a bidentate alkyl phosphine ligand in the synthesis of a fluorescent dye intermediate by olefin hydroformylation, which comprises the following steps: s1: rh (acac) (CO) was added to the reaction flask in sequence2，0.001mmol，0.1mol%, bidentate alkyl phosphine ligand 0.0005mmol, P/Rh =1/1, olefin 1mmol and solvent toluene 1 mL; and (3) putting the reaction bottle into a high-pressure reaction kettle, putting the high-pressure reaction kettle into a constant-temperature oil bath kettle for reaction, and carrying out S2: after the reaction is finished, the mixed solution is transferred into a 25mL glass bottle added with 200 microliters of n-tridecane as an internal standard by using a rubber head dropper, the reaction kettle is cleaned for three times by using a certain amount of dichloromethane, the conversion rate of the olefin is more than 88%, the yield of the aldehyde is more than 72%, and the regioselectivity of the product aldehyde is 80/20-100/0. The application of the one-class bidentate alkyl phosphine ligand in the synthesis of the fluorescent dye intermediate by olefin hydroformylation catalyzes various olefins to carry out hydroformylation reaction by a catalyst consisting of rhodium/bidentate alkyl phosphine ligand, the chemical selectivity of product aldehyde, the sum of the molar ratios of the product aldehyde/isomerized olefin and alkane is 88-100%, the normal-iso ratio of the product aldehyde and the molar ratio of linear chain aldehyde/branched chain aldehyde are 72-99.
Description
Technical Field
The invention relates to the application field of a bidentate alkyl phosphine ligand in synthesis of a fluorescent dye intermediate through olefin hydroformylation, in particular to the application of a bidentate alkyl phosphine ligand in synthesis of a fluorescent dye intermediate through olefin hydroformylation.
Background
The hydroformylation reaction is developed to date, and a plurality of reports aim to solve the chemical/regioselectivity of the product aldehyde, which is mainly reflected in designing and synthesizing a series of phosphine ligands with different electronic/steric hindrance effects to solve the problem, however, the reports of the regulation and control of the hydroformylation reaction of olefin catalyzed by transition metal through bidentate alkyl phosphine ligand are not many, the catalytic effect of the transition metal-bidentate alkyl phosphine ligand catalyst is poor, the universality of the hydroformylation reaction of the rhodium catalyst catalyzed by the existing bidentate alkyl phosphine ligand is poor, the substrate type of the hydroformylation reaction of the rhodium catalyst catalyzed by the bidentate alkyl phosphine ligand is single, the substrate structure of the hydroformylation reaction of the 2, 5-cyclohexadiene substrate catalyzed by the rhodium catalyst catalyzed by the monodentate alkyl phosphine ligand is special, and the universality is not high.
Disclosure of Invention
The invention mainly aims to provide application of a bidentate alkyl phosphine ligand in synthesis of a fluorescent dye intermediate through olefin hydroformylation, and the problems in the background technology can be effectively solved.
In order to achieve the purpose, the invention adopts the technical scheme that:
the application of one-class bidentate alkyl phosphine ligand in synthesis of fluorescent dye intermediate by olefin hydroformylation is that 10mmol of diol substrate, 20mmol of sodium hydride, 20mmol of disubstituted phosphine chloride and 20mL of n-pentane solvent are sequentially added into a sealed tube, the sealed tube is placed in a constant temperature oil bath kettle at the temperature of 90 DEG CAnd (3) the reaction time is 12h, after the reaction is finished, the sealed tube is placed at room temperature for natural cooling, then a large amount of n-pentane is added to filter insoluble substances, the solvent is drained to obtain the target phosphine ligand, the product structure is determined by nuclear magnetic resonance spectroscopy, and the yield of the bidentate alkyl phosphine ligand is generally 60-80%. The hydroformylation process comprises the steps of sequentially adding Rh (acac) (CO) into a reaction bottle20.001mmol, 0.1mol%, bidentate alkyl phosphine ligand 0.0005mmol, P/Rh =1/1, olefin 1mmol and solvent toluene 1mL, placing a reaction bottle into a high-pressure reaction kettle, purging the air in the reaction kettle for three times by using 0.2MPa synthesis gas, purging the synthesis gas to 1MPa, placing the high-pressure kettle into a constant-temperature oil bath kettle, controlling the temperature to be 40 ℃ and the reaction time to be 24h, after the reaction is finished, rapidly placing the high-pressure kettle into ice water to be cooled to room temperature, opening the high-pressure kettle after pressure relief, transferring the mixed solution into a 25mL glass bottle with 200 microliters of n-tridecane as an internal standard by using a rubber head dropper, purging the reaction kettle for three times by using a certain amount of dichloromethane, determining the conversion rate of a substrate and the selectivity of a product by gas chromatography analysis, determining the structure of the product by nuclear magnetic resonance spectroscopy, obtaining olefin with the conversion rate of more than 88% and the yield of aldehyde of more than 72%, the regioselectivity of the product aldehyde is from 80/20 to 100/0.
Preferably, the catalytic reaction process is a hydroformylation reaction of an olefin.
Preferably, the hydroformylation reaction solvent of the olefin may be a common organic solvent such as DMF, DMSO, toluene, THF, N-hexane, N-dimethylacetamide, N-dimethylaniline, and the like, and the preferred solvent is toluene.
Preferably, the catalyst system consists of a rhodium complex and a phosphine ligand, and the reaction system does not contain any additive or auxiliary agent.
Preferably, the olefin is a hydrocarbon compound having one C = C bond, and its kind is not limited, and may be selected from C = C3-C12Linear alpha-olefins, preferably olefins such as 1-pentene, 1-hexene, 1-octene, optionally containing olefins containing said aromatic groups, preferably said olefins are styrene, styrene-propylene, optionally selected from said C5-C8Cyclic internal olefins, preferably the olefin is cyclopentaneAlkene, cyclohexene, cycloheptene, cyclooctene, optionally C5-C8Cyclic heteroatom-containing internal olefins, preferably the olefins are 2, 5-dihydrofuran, 2, 3-dihydrofuran.
Preferably, the transition metal rhodium compound is not limited in kind, e.g. RhCl3、Rh(OAc)3、Rh2O3、Rh(acac)(CO)2、[Rh(OAc)(COD)]2、Rh4(CO)12、Rh6(CO)16、Rh(acac)(CO)2Or [ RhCl (COD)]2Wherein Ac is acetyl, acac is acetylacetone, COD is 1, 5-cyclooctadiene, and the preferred catalyst precursor is Rh (acac) (CO)2The molar ratio of bidentate alkylphosphine ligand to rhodium catalyst is generally from 1 to 50 to 1, preferably from 1 to 10 to 1 and most preferably from 1 to 1.
Preferably, the reaction temperature is generally from room temperature to 150 ℃, more preferably from 30 to 150 ℃, and most preferably 40 ℃, and the total gas pressure of hydrogen and carbon monoxide in the hydroformylation reaction is generally in the range of from 0.1 to 20MPa, preferably from 0.1 to 5MPa, and most preferably 1 MPa.
Preferably, in the synthesis of different bidentate alkylphosphine ligands of examples 1 to 6, the skeleton structure of the bidentate alkylphosphine ligand related to the present invention connected to the oxygen atom may be straight-chain alkyl group with 1 to 6 carbon atoms, etc., the group connected to the phosphorus atom is alkyl group such as tert-butyl group, cyclohexyl group, isopropyl group, etc., and the synthesis of phosphine ligand L1 is embodiment 1; synthesis of phosphine ligand L2 example 2; synthesis of phosphine ligand L3 example 3; synthesis of phosphine ligand L4 example 4; synthesis of phosphine ligand L5 example 5; synthesis of phosphine ligand L6 example 6, the structures of phosphine ligands L1-L6 are as follows:
examples 1-6 the procedure for the synthesis was as follows: sequentially adding 10mmol of diol substrate, 20mmol of sodium hydride, 20mmol of disubstituted phosphine chloride and 20mL of n-pentane solvent into a sealed tube, placing the sealed tube in a constant-temperature oil bath kettle, keeping the temperature at ninety ℃ for 12h, after the reaction is finished, placing the sealed tube at room temperature for natural cooling, then adding a large amount of n-pentane to filter insoluble substances, draining the solvent to obtain the target phosphine ligand, determining the product structure through nuclear magnetic resonance spectroscopy, wherein the yield of the bidentate alkyl phosphine ligand is 60-80%,
examples 7-12 hydroformylation of 2, 5-dihydrofuran with different bidentate alkylphosphine ligands, procedure: rh (acac) (CO) was added to the reaction flask in sequence20.001mmol, 0.1mol%, bidentate alkyl phosphine ligand (P/Rh = 1/1), 1mmol of 2, 5-dihydrofuran and 1mL of solvent toluene, placing a reaction bottle into a high-pressure reaction kettle, aerating and exhausting synthesis gas at 0.2MPa for three times to clean air in the reaction kettle, aerating synthesis gas to 1MPa, placing the high-pressure kettle into a constant-temperature oil bath kettle, controlling the temperature to be 40 ℃ and the reaction time to be 24h, after the reaction is finished, rapidly placing the high-pressure kettle into ice water to be cooled to room temperature, opening the high-pressure kettle after pressure relief, transferring the mixed solution into a 25mL glass bottle added with 200 microliters of n-tridecane as an internal standard by using a rubber head dropper, cleaning the reaction kettle for three times by using a certain amount of dichloromethane, determining the conversion rate of a substrate and the selectivity of the product by gas chromatography, determining the structure of the product by nuclear magnetic resonance spectroscopy, giving out 2 participated by different bidentate alkyl phosphine ligands L1-L6 in Table 1, experimental results of 5-dihydrofuran hydroformylation reaction, 2, 5-dihydrofuran hydroformylation reaction in which different bidentate alkylphosphine ligands L1-L6 participate in Table 1a
| Examples | Phosphine ligands | Conversion ratio (%) of 2, 5-dihydrofuranb | Aldehyde yield (%)b | Aldehyde 2/aldehyde 3 ratiob |
| 7 | L1 | 99 | 99 | 97/3 |
| 8 | L2 | 99 | 99 | 99/1 |
| 9 | L3 | 99 | 99 | 98/2 |
| 10 | L4 | 99 | 97 | 97/3 |
| 11 | L5 | 99 | 94 | 90/10 |
| 12 | L6 | 99 | 92 | 94/6 |
aRh(acac)(CO)2（0.001mmol, 0.1 mol%), bidentate alkylphosphine ligand (P/Rh = 1/1), 1.0mmol of 2, 5-dihydrofuran, 1ml of toluene, CO/H2(1:1)1.0MPa, 40 ℃, 24 hours,bgas chromatography analysis.
Example 13-16 bidentate alkyl phosphine ligand L2 regulates and controls the hydroformylation reaction of 2, 5-dihydrofuran with different rhodium catalysts, the operation steps are as follows: adding 0.001mmol of rhodium catalyst, 0.1mol percent, bidentate alkyl phosphine ligand L2 (0.0005 mmol, P/Rh = 1/1), 1mmol of 2, 5-dihydrofuran and 1mL of solvent toluene into a reaction bottle in sequence, putting the reaction bottle into a high-pressure reaction kettle, filling the air in the reaction kettle with 0.2MPa synthetic gas for three times to clean the air, filling the synthetic gas to 1MPa, putting the high-pressure kettle into a constant-temperature oil bath kettle, keeping the temperature at forty ℃ and the reaction time at 24h, after the reaction is finished, quickly putting the high-pressure kettle into ice water to cool to room temperature, opening the high-pressure kettle after pressure relief, transferring the mixed liquid into a 25mL glass bottle with 200 microliter of n-tridecane as an internal standard by using a dropper, cleaning the reaction kettle with a certain amount of dichloromethane for three times, determining the conversion rate of a substrate and the selectivity of a product by gas chromatography, determining the structure of the product by resonance spectroscopy, table 2 shows that bidentate alkylphosphine ligand L2 regulates the 2, 5-dihydrofuran hydroformylation reaction in which different rhodium catalysts participate, and Table 2 shows that bidentate alkylphosphine ligand L2 regulates the 2, 5-dihydrofuran hydroformylation reaction in which different rhodium catalysts participatea
| Examples | Rhodium catalyst precursor | Conversion ratio (%) of 2, 5-dihydrofuranb | Aldehyde yield (%)b | Aldehyde 2/aldehyde 3 ratiob |
| 13 | RhCl3 | 95 | 93 | 88/12 |
| 14 | [Rh(COD)Cl]2 | 89 | 80 | 91/9 |
| 15 | [Rh(OAc)(COD)]2 | 88 | 84 | 97/3 |
| 16 | Rh2O3 | 90 | 78 | 93/7 |
aRhodium catalyst precursor (0.001 mmol, 0.1 mol%), bidentate alkylphosphine ligand L2 (0.0005 mmol, P/Rh = 1/1), 2, 5-dihydrofuran 1.0mmol, toluene 1ml, CO/H2(1:1)1.0MPa, 40 ℃, 24 hours,bgas chromatography analysis.
Example 17-28 bidentate alkylphosphine ligands L2 Regulation of Rh (acac) (CO)2Catalyzing the hydroformylation reaction of different olefins, and comprising the following operation steps: rh (acac) (CO) was added to the reaction flask in sequence20.001mmol, 0.1mol% and bidentateAlkyl phosphine ligand L2 (P/Rh = 1/1), different types of olefins 1mmol and solvent toluene 1 mL. Putting a reaction bottle into a high-pressure reaction kettle, aerating and discharging 0.2MPa of synthesis gas for three times to clean the air in the reaction kettle, aerating the synthesis gas to 1MPa, putting the high-pressure kettle into a constant-temperature oil bath kettle, keeping the temperature at forty ℃ and the reaction time at 24h, after the reaction is finished, quickly putting the high-pressure kettle into ice water to cool to room temperature, opening the high-pressure kettle after pressure relief, transferring the mixed solution into a 25mL glass bottle with 200 microliters of n-tridecane as an internal standard by using a rubber head dropper, cleaning the reaction kettle for three times by using a certain amount of dichloromethane, determining the conversion rate of a substrate and the selectivity of a product by gas chromatography analysis, determining the structure of the product by nuclear magnetic resonance spectroscopy, and giving a bidentate alkyl phosphine ligand L2 regulation and control Rh (acac) (CO) according to Table 32TABLE 3 bidentate alkylphosphine ligands L2 Regulation of Rh (acac) (CO)2Catalysis of the hydroformylation reaction results of different olefinsa
| Examples | Olefins | Olefin conversion (%)b | (Linear + branched chain) aldehyde yield (%)b | Linear aldehyde/branched aldehyde ratiob |
| 17 | 2, 3-dihydrofurans | 99 | 99 | 95/5 |
| 18 | Cyclopentene | 100 | 97 | -- |
| 19 | Cyclohexene | 99 | 98 | -- |
| 20 | Cycloheptene | 100 | 99 | -- |
| 21 | Cyclooctene | 99 | 99 | -- |
| 22 | 1-pentene | 100 | 87 | 92/8 |
| 23 | 1-hexene | 99 | 69 | 93/7 |
| 24 | 1-heptene | 99 | 72 | 97/3 |
| 25 | 1-octene | 99 | 99 | 84/16 |
| 26 | 2-octene | 98 | 99 | 80/20 |
| 27 | Styrene (meth) acrylic acid ester | 99 | 99 | 5/95 |
| 28 | Styrene-acrylic resin | 99 | 99 | 88/12 |
aRh(acac)(CO)2(0.001 mmol, 0.1 mol%), bidentate alkylphosphine ligand L2 (0.0005 mmol, P/Rh = 1/1), substrate olefin 1.0mmol, toluene 1mL, CO/H2(1:1)1.0MPa, 40 ℃, 24 hours,bgas chromatography analysis. Attaching a first component: the reaction of the present invention requires detailed information of the procedure when detecting by a gas chromatograph as follows: HP-5, -60oC-325oC，30m*320μm*0.25μm, sample introduction amount: 1μL, a sample inlet: a heater: 250oC, pressure: 4.9551psi, total flow: 124mL/min, septum purge flow: 3mL/min, split ratio: 120:1, split flow: 120mL/min, column: flow rate: 1mL/min, pressure: 4.9551psi, average linear velocity: 19.418cm/sec, retention time: 2.6112min, post run: 6.5mL/min, column box: column box opening temperature: 50oC, balance time: 0.5min, maximum column box temperature: 325oC, post-operation: 50oC, post-run time: 0min, temperature rising program: initial value: rate of 0oC/min, value 50oC, keeping time of 0.1min, running time of 0.1min, gradient 1: rate of 15oC/min, value 150oC, holding time of 0.2min, running time of 6.9667min, gradient 2: rate of 100oC/min, value 215oC, keeping time of 5min, running time of 12.617min, detector: front FID: a heater: 300oC, air flow rate: 400mL/min, hydrogen gas flow: 30mL/min, tail gas blowing flow: 25mL/min, column flow: 25mL/min, flame: 25.1pA, post TCD: a heater: 300oC, reference flow rate: 10mL/min, tail gas blowing flow: 5mL/min, hot wire: 0(25μV)。
Compared with the prior art, the invention has the following beneficial effects:
in the invention, the catalyst consisting of rhodium/bidentate alkyl phosphine ligand is used for catalyzing various olefins to carry out hydroformylation reaction, the chemical selectivity of product aldehyde, the sum of the molar ratio of the product aldehyde is 88-100%, the positive-iso ratio of the product aldehyde and the molar ratio of linear chain aldehyde/branched chain aldehyde is 72-99, which are all very excellent, the method for regulating and controlling the hydroformylation reaction by designing and synthesizing the novel bidentate alkyl phosphine ligand to efficiently convert the olefins into products with higher added values can overcome the defect that the chemical/regional selectivity is difficult to control reported in literature, the cost of the industrial production of hydroformylation of various olefins is reduced, a new method is provided for the large-scale production of fluorescent dye intermediates, and a new method is also provided for the production of bulk chemicals related to the field of petrochemical industry.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention relates to an application of a bidentate alkyl phosphine ligand in synthesis of a fluorescent dye intermediate by olefin hydroformylation, which comprises the following steps:
s1: adding 10mmol of diol substrate, 20mmol of sodium hydride, 20mmol of disubstituted phosphine chloride and 20mL of n-pentane solvent into the sealed tube in sequence, placing the sealed tube in a constant-temperature oil bath kettle, the temperature is 90 ℃, the reaction time is 12h, after the reaction is finished, the sealed tube is placed at the room temperature for natural cooling, then adding a large amount of n-pentane to filter insoluble substances, pumping out the solvent to obtain a target phosphine ligand, determining the product structure through nuclear magnetic resonance spectroscopy, the yield of the bidentate alkyl phosphine ligand is 60-80% generally, the hydroformylation reaction solvent of the olefin can be DMF, DMSO, toluene, THF, N-hexane, N-dimethylacetamide, N-dimethylaniline and other common organic solvents, the preferable solvent is toluene, the catalytic reaction process is the hydroformylation reaction of the olefin, the catalyst system is composed of a rhodium complex and a phosphine ligand, and the reaction system does not contain any additive or auxiliary agent.
S2: the hydroformylation reaction temperature is generally from room temperature to 150 ℃, more preferably from 30 to 150 ℃, and most preferably 40 ℃, and the total gas pressure of hydrogen and carbon monoxide in the hydroformylation reaction is generally from 0.1 to 20MPa, preferably from 0.1 to 5MPa, and most preferably 1 MPa.
S3: the olefin used in the hydroformylation reaction is a hydrocarbon compound having one C = C bond, and the kind thereof is not limited, and may be selected from C = C3-C12Linear alpha-olefins, preferably olefins such as 1-pentene, 1-hexene, 1-octene, optionally containing aromatic groups, preferably olefins such as styrene, styrene-propylene, optionally C5-C8Cyclic internal olefins, preferably olefinsIs cyclopentene, cyclohexene, cycloheptene, cyclooctene, and is selected from C5-C8The preferred internal olefins containing heteroatoms in the ring are 2, 5-dihydrofuran and 2, 3-dihydrofuran.
S4: the kind of transition metal rhodium compound is not limited, e.g. RhCl3、Rh(OAc)3、Rh2O3、Rh(acac)(CO)2、[Rh(OAc)(COD)]2、Rh4(CO)12、Rh6(CO)16、Rh(acac)(CO)2Or [ RhCl (COD)]2Where Ac is acetyl, acac is acetylacetone, COD is 1, 5-cyclooctadiene, preferred catalyst precursors are Rh (acac) (CO)2The molar ratio of bidentate alkylphosphine ligand to rhodium catalyst is generally from 1 to 50 to 1, preferably from 1 to 10 to 1 and most preferably from 1 to 1.
S5: rh (acac) (CO) was added to the reaction flask in sequence20.001mmol, 0.1mol%, bidentate alkylphosphine ligand 0.0005mmol, P/Rh =1/1, olefin 1mmol, and solvent toluene 1 mL.
S6: placing a reaction bottle into a high-pressure reaction kettle, inflating and deflating 0.2MPa of synthesis gas for three times to clean the air in the reaction kettle, refilling the synthesis gas to 1MPa, placing the high-pressure kettle into a constant-temperature oil bath kettle, controlling the temperature to be 40 ℃, controlling the reaction time to be 24h, after the reaction is finished, rapidly placing the high-pressure kettle into ice water to be cooled to room temperature, opening the high-pressure kettle after pressure relief, transferring the mixed solution into a 25mL glass bottle added with 200 microliters of n-tridecane as an internal standard by using a rubber head dropper, cleaning the reaction kettle for three times by using a certain amount of dichloromethane, determining the conversion rate of a substrate and the selectivity of a product by gas chromatography analysis, and determining the structure of the product by nuclear magnetic resonance spectroscopy.
S7: the conversion rate of the obtained olefin is more than 88 percent, the yield of the aldehyde is more than 72 percent, the regioselectivity of the product aldehyde is 80/20 to 100/0, and the synthesis of different bidentate alkyl phosphine ligands in examples 1 to 6 can be carried out, wherein the skeleton structure of the bidentate alkyl phosphine ligand connected with an oxygen atom can be straight-chain alkyl with 1 to 6 carbon atoms and the like, the group connected with a phosphorus atom is an alkyl group such as tert-butyl, cyclohexyl, isopropyl and the like, and the synthesis of the phosphine ligand L1 is carried out in example 1; synthesis of phosphine ligand L2 example 2; synthesis of phosphine ligand L3 example 3; synthesis of phosphine ligand L4 example 4; synthesis of phosphine ligand L5 example 5; synthesis of phosphine ligand L6 example 6, the structures of phosphine ligands L1-L6 are as follows:
examples 1-6 the procedure for the synthesis was as follows: adding 10mmol of diol substrate, 20mmol of sodium hydride and 20mL of n-pentane solvent into a sealed tube in sequence, placing the sealed tube in a constant-temperature oil bath pan, keeping the temperature at ninety ℃ and the reaction time at 12h, after the reaction is finished, placing the sealed tube at room temperature for natural cooling, then adding a large amount of n-pentane to filter insoluble substances, draining the solvent to obtain the target phosphine ligand, determining the product structure through nuclear magnetic resonance spectroscopy, wherein the yield of the bidentate alkyl phosphine ligand is 60-80%.
Examples 7-12 hydroformylation of 2, 5-dihydrofuran with different bidentate alkylphosphine ligands, procedure: rh (acac) (CO) was added to the reaction flask in sequence20.001mmol, 0.1mol%, bidentate alkyl phosphine ligand (P/Rh = 1/1), 1mmol of 2, 5-dihydrofuran and 1mL of solvent toluene, placing a reaction bottle into a high-pressure reaction kettle, aerating and exhausting synthesis gas at 0.2MPa for three times to clean air in the reaction kettle, aerating synthesis gas to 1MPa, placing the high-pressure kettle into a constant-temperature oil bath kettle, controlling the temperature to be 40 ℃ and the reaction time to be 24h, after the reaction is finished, rapidly placing the high-pressure kettle into ice water to be cooled to room temperature, opening the high-pressure kettle after pressure relief, transferring the mixed solution into a 25mL glass bottle added with 200 microliters of n-tridecane as an internal standard by using a rubber head dropper, cleaning the reaction kettle for three times by using a certain amount of dichloromethane, determining the conversion rate of a substrate and the selectivity of the product by gas chromatography, determining the structure of the product by nuclear magnetic resonance spectroscopy, giving out 2 participated by different bidentate alkyl phosphine ligands L1-L6 in Table 1, experimental results of 5-dihydrofuran hydroformylation reaction, 2, 5-dihydrofuran hydroformylation reaction in which different bidentate alkylphosphine ligands L1-L6 participate in Table 1a
| Examples | Phosphine ligands | Conversion ratio (%) of 2, 5-dihydrofuranb | Aldehyde yield (%)b | Aldehyde 2/aldehyde 3 ratiob |
| 7 | L1 | 99 | 99 | 97/3 |
| 8 | L2 | 99 | 99 | 99/1 |
| 9 | L3 | 99 | 99 | 98/2 |
| 10 | L4 | 99 | 97 | 97/3 |
| 11 | L5 | 99 | 94 | 90/10 |
| 12 | L6 | 99 | 92 | 94/6 |
aRh(acac)(CO)2(0.001 mmol, 0.1 mol%), bidentate alkylphosphine ligand (P/Rh = 1/1), 2, 5-dihydrofuran 1.0mmol, toluene 1ml, CO/H2(1:1)1.0MPa, 40 ℃, 24 hours,bgas chromatography analysis.
Example 13-16 bidentate alkyl phosphine ligand L2 regulates and controls the hydroformylation reaction of 2, 5-dihydrofuran with different rhodium catalysts, the operation steps are as follows: adding 0.001mmol of rhodium catalyst, 0.1mol percent, bidentate alkyl phosphine ligand L2 (0.0005 mmol, P/Rh = 1/1), 1mmol of 2, 5-dihydrofuran and 1mL of solvent toluene into a reaction bottle in sequence, putting the reaction bottle into a high-pressure reaction kettle, filling the air in the reaction kettle with 0.2MPa synthetic gas for three times to clean the air, filling the synthetic gas to 1MPa, putting the high-pressure kettle into a constant-temperature oil bath kettle, keeping the temperature at forty ℃ and the reaction time at 24h, after the reaction is finished, quickly putting the high-pressure kettle into ice water to cool to room temperature, opening the high-pressure kettle after pressure relief, transferring the mixed liquid into a 25mL glass bottle with 200 microliter of n-tridecane as an internal standard by using a dropper, cleaning the reaction kettle with a certain amount of dichloromethane for three times, determining the conversion rate of a substrate and the selectivity of a product by gas chromatography, determining the structure of the product by resonance spectroscopy, table 2 shows that bidentate alkylphosphine ligand L2 regulates the 2, 5-dihydrofuran hydroformylation reaction in which different rhodium catalysts participate, and Table 2 shows that bidentate alkylphosphine ligand L2 regulates the 2, 5-dihydrofuran hydroformylation reaction in which different rhodium catalysts participatea
| Examples | Rhodium catalyst precursor | Conversion ratio (%) of 2, 5-dihydrofuranb | Aldehyde yield (%)b | Aldehyde 2/aldehyde 3 ratiob |
| 13 | RhCl3 | 95 | 93 | 88/12 |
| 14 | [Rh(COD)Cl]2 | 89 | 80 | 91/9 |
| 15 | [Rh(OAc)(COD)]2 | 88 | 84 | 97/3 |
| 16 | Rh2O3 | 90 | 78 | 93/7 |
aRhodium catalyst precursor (0.001 mmol, 0.1 mol%), bidentate alkylphosphine ligand L2 (0.0005 mmol, P/Rh = 1/1), 2, 5-dihydrofuran 1.0mmol, toluene 1ml, CO/H2(1:1)1.0MPa, 40 ℃, 24 hours,bgas chromatography analysis.
Example 17-28 bidentate alkylphosphine ligands L2 Regulation of Rh (acac) (CO)2Catalyzing the hydroformylation reaction of different olefins, and comprising the following operation steps: rh (acac) (CO) was added to the reaction flask in sequence20.001mmol, 0.1mol%, bidentate alkylphosphine ligand L2 (P/Rh = 1/1), 1mmol of a different type of olefin and 1mL of the solvent toluene. Putting a reaction bottle into a high-pressure reaction kettle, aerating and discharging 0.2MPa of synthesis gas for three times to clean the air in the reaction kettle, aerating the synthesis gas to 1MPa, putting the high-pressure kettle into a constant-temperature oil bath kettle, keeping the temperature at forty ℃ and the reaction time at 24h, after the reaction is finished, quickly putting the high-pressure kettle into ice water to cool to room temperature, opening the high-pressure kettle after pressure relief, transferring the mixed solution into a 25mL glass bottle with 200 microliters of n-tridecane as an internal standard by using a rubber head dropper, cleaning the reaction kettle for three times by using a certain amount of dichloromethane, determining the conversion rate of a substrate and the selectivity of a product by gas chromatography analysis, determining the structure of the product by nuclear magnetic resonance spectroscopy, and giving a bidentate alkyl phosphine ligand L2 regulation and control Rh (acac) (CO) according to Table 32TABLE 3 bidentate alkylphosphine ligands L2 Regulation of Rh (acac) (CO)2Catalysis of the hydroformylation reaction results of different olefinsa
| Examples | Olefins | Olefin conversion (%)b | (Linear + branched chain) aldehyde yield (%)b | Linear aldehyde/branched aldehyde ratiob |
| 17 | 2, 3-dihydrofurans | 99 | 99 | 95/5 |
| 18 | Cyclopentene | 100 | 97 | -- |
| 19 | Cyclohexene | 99 | 98 | -- |
| 20 | Cycloheptene | 100 | 99 | -- |
| 21 | Cyclooctene | 99 | 99 | -- |
| 22 | 1-pentene | 100 | 87 | 92/8 |
| 23 | 1-hexene | 99 | 69 | 93/7 |
| 24 | 1-heptene | 99 | 72 | 97/3 |
| 25 | 1-octene | 99 | 99 | 84/16 |
| 26 | 2-octene | 98 | 99 | 80/20 |
| 27 | Styrene (meth) acrylic acid ester | 99 | 99 | 5/95 |
| 28 | Styrene-acrylic resin | 99 | 99 | 88/12 |
aRh(acac)(CO)2(0.001 mmol, 0.1 mol%), bidentate alkylphosphine ligand L2 (0.0005 mmol, P/Rh = 1/1), substrate olefin 1.0mmol, toluene 1mL, CO/H2(1:1)1.0MPa, 40 ℃, 24 hours,bgas chromatography analysis.
Attached: the reaction of the present invention requires detailed information of the procedure when detecting by a gas chromatograph as follows: HP-5, -60oC-325oC，30m*320μm*0.25μm, sample introduction amount: 1μL, a sample inlet: a heater: 250oC, pressure: 4.9551psi, total flow: 124mL/min, septum purge flow: 3mL/min, split ratio: 120:1, split flow: 120mL/min, column: flow rate: 1mL/min, pressure: 4.9551psi, average linear velocity: 19.418cm/sec, retention time: 2.6112min, post run: 6.5mL/min, column box: column box opening temperature: 50oC, balance time: 0.5min, maximum column box temperature: 325oC, post-operation: 50oC, post-run time: 0min, temperature rising program: initial value: rate of 0oC/min, value 50oC, keeping time of 0.1min, running time of 0.1min, gradient 1: rate of 15oC/min, value 150oC, holding time of 0.2min, running time of 6.9667min, gradient 2: rate of 100oC/min, value 215oC, keeping time of 5min, running time of 12.617min, detector: front FID: a heater: 300oC, air flow rate: 400mL/min, hydrogen gas flow: 30mL/min, tail gas blowing flow: 25mL/min, column flow: 25mL/min, flame: 25.1pA, post TCD: a heater: 300oC, reference flow rate: 10mL/min, tail gas blowing flow: 5mL/min, hot wire: 0(25μV)。
The invention uses one-class bidentate alkyl phosphine ligand in the application of olefin hydroformylation synthesis fluorescent dye intermediate, uses the catalyst formed by rhodium/bidentate alkyl phosphine ligand to catalyze various olefins to carry out hydroformylation reaction, the chemical selectivity of the product aldehyde, the sum of the molar ratio of the product aldehyde/isomerized olefin and alkane is 88-100%, the normal-iso ratio of the product aldehyde and the molar ratio of the straight chain aldehyde/branched chain aldehyde are 72-99, which are all excellent, the method for regulating and controlling the hydroformylation reaction by designing and synthesizing the novel bidentate alkyl phosphine ligand to efficiently convert the olefin into the product with higher added value can overcome the defect that the chemical/regional selectivity reported by the literature is difficult to control, reduce the cost of the industrialized production of various olefin hydroformylation, and provide a new method for the large-scale production of the fluorescent dye intermediate, also provides a new method for producing bulk chemicals related to the field of petrochemical industry.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The application of one type of bidentate alkyl phosphine ligand in the synthesis of fluorescent dye intermediates by olefin hydroformylation is characterized in that: the method comprises the following operation steps:
s1: adding 10mmol of diol substrate, 20mmol of sodium hydride, 20mmol of disubstituted phosphine chloride and 20mL of n-pentane solvent into the sealed tube in sequence;
s2: placing the sealed tube in a constant-temperature oil bath kettle, wherein the temperature is 90 ℃, the reaction time is 12h, and after the reaction is finished, placing the sealed tube at room temperature for natural cooling;
s3: then adding a large amount of n-pentane to filter insoluble substances, draining the solvent to obtain a target phosphine ligand, and determining the product structure through nuclear magnetic resonance spectroscopy;
s4: the yield of the bidentate alkyl phosphine ligand is 60-80% generally;
s5: rh (acac) (CO) was added to the reaction flask in sequence20.001mmol, 0.1mol%, bidentate alkyl phosphine ligand 0.0005mmol, P/Rh =1/1, olefin 1mmol and solvent toluene 1 mL;
s6: placing a reaction bottle into a high-pressure reaction kettle, inflating and deflating 0.2MPa of synthesis gas for three times to clean the air in the reaction kettle, refilling the synthesis gas to 1MPa, placing the high-pressure kettle into a constant-temperature oil bath kettle, controlling the temperature to be 40 ℃, controlling the reaction time to be 24h, after the reaction is finished, rapidly placing the high-pressure kettle into ice water to be cooled to room temperature, opening the high-pressure kettle after pressure relief, transferring the mixed solution into a 25mL glass bottle added with 200 microliters of n-tridecane as an internal standard by using a rubber head dropper, cleaning the reaction kettle for three times by using a certain amount of dichloromethane, determining the conversion rate of a substrate and the selectivity of a product by gas chromatography analysis, and determining the structure of the product by nuclear magnetic resonance spectroscopy;
s7: olefin conversions of greater than 88% and aldehyde yields of greater than 72% were obtained with regioselectivities for the product aldehydes of 80/20 to 100/0.
2. The use of a bidentate alkyl phosphine ligand of claim 1 in the hydroformylation of olefins to synthesize fluorescent dye intermediates, wherein: the catalytic reaction process is a hydroformylation reaction of an olefin.
3. The use of a bidentate alkyl phosphine ligand of claim 1 in the hydroformylation of olefins to synthesize fluorescent dye intermediates, wherein: the hydroformylation solvent of the olefin may be a common organic solvent such as DMF, DMSO, toluene, THF, N-hexane, N-dimethylacetamide, N-dimethylaniline, and the like, and the preferred solvent is toluene.
4. The use of a bidentate alkyl phosphine ligand of claim 1 in the hydroformylation of olefins to synthesize fluorescent dye intermediates, wherein: the catalyst system consists of a rhodium complex and a phosphine ligand, and the reaction system does not contain any additive or auxiliary agent.
5. The use of a bidentate alkyl phosphine ligand of claim 1 in the hydroformylation of olefins to synthesize fluorescent dye intermediates, wherein: the olefin is a hydrocarbon compound having one C = C bond, and its kind is not limited, and may be selected from C = C3-C12The linear alpha-olefins, preferably the olefins, are 1-pentene, 1-hexene, 1-octene, optionally selected from olefins containing said aromatic group, preferably said olefins are styrene, styrene-propylene, optionally selected from said C5-C8Cyclic internal olefins, preferably said olefins are cyclopentene, cyclohexene, cycloheptene, cyclooctene, which may be selected from said C5-C8Cyclic heteroatom-containing internal olefins, preferably the olefins are 2, 5-dihydrofuran, 2, 3-dihydrofuran.
6. The use of a bidentate alkyl phosphine ligand of claim 1 in the hydroformylation of olefins to synthesize fluorescent dye intermediates, wherein: the transition metal rhodium compound is not limited in kind, for example RhCl3、Rh(OAc)3、Rh2O3、Rh(acac)(CO)2、[Rh(OAc)(COD)]2、Rh4(CO)12、Rh6(CO)16、Rh(acac)(CO)2Or [ RhCl (COD)]2Wherein Ac is acetyl, acac is acetylacetone, COD is 1, 5-cyclooctadiene, and the preferred catalyst precursor is Rh (acac) (CO)2，The molar ratio of bidentate alkylphosphine ligand to rhodium catalyst is generally from 1 to 50 to 1, preferably from 1 to 10 to 1, most preferably from 1 to 1.
7. The use of a bidentate alkyl phosphine ligand of claim 1 in the hydroformylation of olefins to synthesize fluorescent dye intermediates, wherein: the reaction temperature is generally from room temperature to 150 ℃, more preferably from 30 to 150 ℃, and most preferably 40 ℃, and the total gas pressure of hydrogen and carbon monoxide in the hydroformylation reaction is generally in the range of from 0.1 to 20MPa, preferably from 0.1 to 5MPa, and most preferably 1 MPa.
8. The use of a bidentate alkyl phosphine ligand of claim 1 in the hydroformylation of olefins to synthesize fluorescent dye intermediates, wherein: in the examples 1 to 6, the skeleton structure of the bidentate alkylphosphine ligand connected to the oxygen atom may be straight-chain alkyl group having 1 to 6 carbon atoms, etc., the group connected to the phosphorus atom may be an alkyl group such as tert-butyl group, cyclohexyl group, isopropyl group, etc., and the synthesis of the phosphine ligand L1 is described in example 1; synthesis of phosphine ligand L2 example 2; synthesis of phosphine ligand L3 example 3; synthesis of phosphine ligand L4 example 4; synthesis of phosphine ligand L5 example 5; synthesis of phosphine ligand L6 example 6, the structures of phosphine ligands L1-L6 are as follows:
examples 1-6 the procedure for the synthesis was as follows: sequentially adding 10mmol of diol substrate, 20mmol of sodium hydride and 20mL of n-pentane solvent into a sealed tube, placing the sealed tube in a constant-temperature oil bath pan, reacting at ninety ℃ for 12h, naturally cooling the sealed tube at room temperature after the reaction is finished, adding a large amount of n-pentane to filter insoluble substances, draining the solvent to obtain a target phosphine ligand, determining the product structure through nuclear magnetic resonance spectroscopy, wherein the yield of the bidentate alkyl phosphine ligand is 60-80%,
examples 7-12 hydroformylation of 2, 5-dihydrofuran with different bidentate alkylphosphine ligands, procedure: rh (acac) (CO) was added to the reaction flask in sequence20.001mmol, 0.1mol%, bidentate alkyl phosphine ligand (P/Rh = 1/1), 1mmol of 2, 5-dihydrofuran and 1mL of solvent toluene, placing a reaction bottle into a high-pressure reaction kettle, aerating and exhausting synthesis gas at 0.2MPa for three times to clean air in the reaction kettle, aerating synthesis gas to 1MPa, placing the high-pressure kettle into a constant-temperature oil bath kettle, controlling the temperature to be 40 ℃ and the reaction time to be 24h, after the reaction is finished, rapidly placing the high-pressure kettle into ice water to be cooled to room temperature, opening the high-pressure kettle after pressure relief, transferring the mixed solution into a 25mL glass bottle added with 200 microliters of n-tridecane as an internal standard by using a rubber head dropper, cleaning the reaction kettle for three times by using a certain amount of dichloromethane, determining the conversion rate of a substrate and the selectivity of the product by gas chromatography, determining the structure of the product by nuclear magnetic resonance spectroscopy, giving out 2 participated by different bidentate alkyl phosphine ligands L1-L6 in Table 1, experimental results of 5-dihydrofuran hydroformylation reaction, 2, 5-dihydrofuran hydroformylation reaction in which different bidentate alkylphosphine ligands L1-L6 participate in Table 1a
aRh(acac)(CO)2(0.001 mmol, 0.1 mol%), bidentate alkylphosphine ligand (P/Rh = 1/1), 2, 5-dihydrofuran 1.0mmol, toluene 1ml, CO/H2(1:1)1.0MPa, 40 ℃, 24 hours,bgas chromatography analysis shows that in the embodiment 13-16, bidentate alkyl phosphine ligands L2 regulate and control the hydroformylation reaction of 2, 5-dihydrofuran in which different rhodium catalysts participate, the operation steps are as follows: adding 0.001mmol of rhodium catalyst, 0.1mol percent, bidentate alkyl phosphine ligand L2 (0.0005 mmol, P/Rh = 1/1), 1mmol of 2, 5-dihydrofuran and 1mL of solvent toluene into a reaction bottle in sequence, putting the reaction bottle into a high-pressure reaction kettle, filling the air in the reaction kettle with 0.2MPa synthetic gas for three times to clean the air, filling the synthetic gas to 1MPa, putting the high-pressure kettle into a constant-temperature oil bath kettle, keeping the temperature at forty ℃ and the reaction time at 24h, after the reaction is finished, quickly putting the high-pressure kettle into ice water to cool to room temperature, opening the high-pressure kettle after pressure relief, transferring the mixed liquid into a 25mL glass bottle with 200 microliter of n-tridecane as an internal standard by using a dropper, cleaning the reaction kettle with a certain amount of dichloromethane for three times, determining the conversion rate of a substrate and the selectivity of a product by gas chromatography, determining the structure of the product by resonance spectroscopy, table 2 shows that bidentate alkylphosphine ligand L2 regulates the 2, 5-dihydrofuran hydroformylation reaction in which different rhodium catalysts participate, and Table 2 shows that bidentate alkylphosphine ligand L2 regulates the 2, 5-dihydrofuran hydroformylation reaction in which different rhodium catalysts participatea
aRhodium catalyst precursor (0.001 mmol, 0.1 mol%), bidentate alkylphosphine ligand L2 (0.0005 mmol, P/Rh = 1/1), 2, 5-dihydrofuran 1.0mmol, toluene 1ml, CO/H2(1:1)1.0MPa, 40 ℃, 24 hours,bgas chromatography analysis, examples 17-28 bidentate alkylphosphine ligands L2 Regulation of Rh (acac) (CO)2Catalyzing the hydroformylation reaction of different olefins, and comprising the following operation steps: sequentially adding into a reaction flaskRh (acac) (CO)20.001mmol, 0.1mol%, bidentate alkyl phosphine ligand L2 (P/Rh = 1/1), 1mmol of different types of olefins and 1mL of solvent toluene, placing a reaction bottle into a high-pressure reaction kettle, charging and discharging 0.2MPa of synthetic gas for three times to clean the air in the reaction kettle, charging the synthetic gas to 1MPa, placing the high-pressure kettle in a constant-temperature oil bath kettle, the temperature is forty ℃, the reaction time is 24h, after the reaction is finished, the high-pressure kettle is quickly placed into ice water to be cooled to the room temperature, the high-pressure kettle is opened after pressure relief, the mixed solution is transferred into a 25mL glass bottle added with 200 microliters of n-tridecane as an internal standard by a rubber head dropper, the reaction kettle is washed three times by a certain amount of dichloromethane, substrate conversion and product selectivity were determined by gas chromatographic analysis and product structure determined by nuclear magnetic resonance spectroscopy, with Table 3 giving bidentate alkylphosphine ligand L2 modulating Rh (acac) (CO).2TABLE 3 results of the hydroformylation of different olefins catalyzed by bidentate alkylphosphine ligands L2 Regulation of Rh (acac) (CO)2Catalysis of the hydroformylation reaction results of different olefinsa
aRh(acac)(CO)2(0.001 mmol, 0.1 mol%), bidentate alkylphosphine ligand L2 (0.0005 mmol, P/Rh = 1/1), substrate olefin 1.0mmol, toluene 1mL, CO/H2(1:1)1.0MPa, 40 ℃, 24 hours,bgas chromatography, attached: the reaction of the present invention requires detailed information of the procedure when detecting by a gas chromatograph as follows: HP-5, -60oC-325oC，30m*320μm*0.25μm, sample introduction amount: 1μL, a sample inlet: a heater: 250oC, pressure: 4.9551psi, total flow: 124mL/min, septum purge flow: 3mL/min, split ratio: 120:1, split flow: 120mL/min, column: flow rate: 1mL/min, pressure: 4.9551psi, average linear velocity: 19.418cm/sec, retention time: 2.6112min, post run: 6.5mL/min, column box: column box opening temperature: 50oC, balance time: 0.5min, maximum column box temperature: 325oC, post-operation:50oc, post-run time: 0min, temperature rising program: initial value: rate of 0oC/min, value 50oC, keeping time of 0.1min, running time of 0.1min, gradient 1: rate of 15oC/min, value 150oC, holding time of 0.2min, running time of 6.9667min, gradient 2: rate of 100oC/min, value 215oC, keeping time of 5min, running time of 12.617min, detector: front FID: a heater: 300oC, air flow rate: 400mL/min, hydrogen gas flow: 30mL/min, tail gas blowing flow: 25mL/min, column flow: 25mL/min, flame: 25.1pA, post TCD: a heater: 300oC, reference flow rate: 10mL/min, tail gas blowing flow: 5mL/min, hot wire: 0(25μV)。
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