CN110963902A - Method for synthesizing R-citronellal by water-oil two-phase asymmetric hydrogenation and catalyst used in method - Google Patents

Method for synthesizing R-citronellal by water-oil two-phase asymmetric hydrogenation and catalyst used in method Download PDF

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CN110963902A
CN110963902A CN201911237004.0A CN201911237004A CN110963902A CN 110963902 A CN110963902 A CN 110963902A CN 201911237004 A CN201911237004 A CN 201911237004A CN 110963902 A CN110963902 A CN 110963902A
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catalyst
metal precursor
citronellal
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CN110963902B (en
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谢硕
黄文学
沈稳
张永振
董菁
于磊
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Wanhua Chemical Group Co Ltd
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    • B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
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Abstract

The invention provides a method for synthesizing R-citronellal by water-oil two-phase asymmetric hydrogenation and a catalyst used in the method, and particularly relates to a method for obtaining R-citronellal by asymmetrically hydrogenating neral or geranial in a water-oil two-phase system by using hydrogen as a reducing agent and a water-soluble metal complex as a catalyst. The method has the main advantages that the water-soluble phosphine ligand is used, so that the catalyst has good water solubility, the reaction is carried out in a water-oil two-phase system, and the separation of the product R-citronellal and the catalyst can be realized by simple phase separation after the hydrogenation reaction is finished; in addition, a small amount of lithium salt is added into the reaction system, so that the enantioselectivity of the product is improved. Finally, the catalyst dissolved in water can be recycled for many times, so that the catalyst cost is greatly reduced.

Description

Method for synthesizing R-citronellal by water-oil two-phase asymmetric hydrogenation and catalyst used in method
Technical Field
The invention belongs to the field of fine chemical industry and flavors and fragrances, and particularly relates to a method for synthesizing R-citronellal by asymmetrically hydrogenating citral in a water-oil two-phase system and a catalyst used in the method.
Background
Citronellal is a chain-shaped monoterpene aldehyde, naturally exists in citronella oil and eucalyptus citriodora oil, has strong and fresh citrus breath, can be used for preparing citrus and cherry essence and can also be used for preparing soap essence, the consumption of citronellal in the two aspects is small, and more citronellal is used for synthesizing cooling agents such as menthol, mentha-carboxamide and the like. Due to the fact that the molecular structure of the L-menthol derivative has a chiral center, citronellal has two optical isomers of (R) -citronellal and (S) -citronellal, wherein the (R) -citronellal can be used for synthesizing natural L-menthol, and therefore the L-menthol derivative has higher economic value. Chiral synthesis of (R) -citronellal has attracted attention since a long time, and over the course of many years of effort, chemists have developed various chiral synthesis methods for (R) -citronellal, including asymmetric hydrogenation of neral or geranial, myrcene, dehydrogenation of chiral citronellol, isomerization of nerol or geraniol, and the like. Among the synthetic methods of citronellal, the neral or geranial asymmetric hydrogenation method has the advantages of easily available raw materials, simple reaction and good chiral control, and is the most studied synthetic method of chiral citronellal by people at present.
As early as 1982, Varagnat et al achieved asymmetric hydrogenation of neral and geranial using rhodium carbonyl and chiral bisphosphine ligands, yielding chiral citronellal products in good yields up to 71% ee value (J.mol.Cat.1982,16, 51). In patent CN101932543, neral and geranial are separated by distillation, and then neral or geranial is reduced by rhodium and chiral diphosphine ligand in hydrogen atmosphere containing part of carbon monoxide to obtain chiral citronellal product, ee value can reach 90% at most, in an example reported in which a continuous hydrogenation reaction is performed, S/C reaches 10941 at most.
Figure BDA0002305152980000011
Patents CN102458659 and CN103249484 adopt metal powders or supported metal catalysts of groups 8 to 10, such as palladium carbon, palladium alumina, etc., under the concerted catalysis of chiral cyclic amine and acid, the asymmetric hydrogenation of citral is realized, chiral citronellal is obtained, and ee is up to 91%.
Figure BDA0002305152980000012
Patent CN101932543 utilizes chiral rhodium catalyst, under the action of additives such as sodium iodide, tetra-n-octylammonium bromide, phenyltriethylammonium chloride, etc., to implement asymmetric hydrogenation of neral or geranial, the optical purity of the obtained citronellal is 72-98%, and the yield can reach 71-99%. The patent CN106086089A utilizes an enzyme method to asymmetrically reduce citral, combines amino acid catalyzed citral cis-trans isomerization with saccharomyces cerevisiae enol reductase OYE1 catalyzed citral asymmetric reduction reaction, and obtains a chiral citronellal product. When the reductase OYE1 is reduced, neral reacts to obtain (S) -citronellal, geranial reacts to obtain (R) -citronellal, the reduction speed of the geranial is higher than that of the neral, and the ee value of the citronellal can reach 65.4 percent at most.
In summary, although there are many reports on chiral citronellal obtained by asymmetric reduction of citral at present, these reports basically adopt expensive metal rhodium catalyst and chiral diphosphine ligand, the catalyst not only has large dosage, but also after the reaction is finished, the catalyst can not be recovered, or the recovery and reuse conditions are harsh, the flow is complex, so the economic cost is high, and the benefit is poor. In order to reduce the cost of R-citronellal, a high-efficiency citral asymmetric hydrogenation system needs to be developed, so that the cost of the catalyst is reduced, and better economic benefit is brought.
Disclosure of Invention
The invention aims to provide a catalyst and a method for synthesizing R-citronellal by asymmetric hydrogenation in water and oil phases.
According to a first aspect of the present invention, there is provided a process for the asymmetric hydrogenation of R-citronellal in a two-phase water-oil phase, which comprises: hydrogen is used as a reducing agent, a water-soluble metal complex is used as a catalyst, and neral or geranial is asymmetrically hydrogenated in a water-oil two-phase system to obtain R-citronellal; after the reaction is finished, separating citronellal and the catalyst by oil-water split-phase separation;
the water-soluble metal complex comprises a metal precursor and a water-soluble ligand,
wherein the metal precursor has the formula [ M (X) Y]Wherein M represents a metal ion including, but not limited to, ruthenium, rhodium, iridium, nickel, palladium, platinum, osmium, manganese, cobalt, iron, and the like, preferably rhodium metal; x represents a coordinating group including, but not limited to, ethylene, 1, 4-cyclooctadiene, norbornadiene, p-cymene, carbon monoxide, and the like, preferably carbon monoxide, 1, 4-cyclooctadiene, and norbornadiene; y represents an anion including, but not limited to, fluorine, chlorine, bromine, iodine, trifluoromethanesulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, methoxide, acetylacetone, acetate, and the like. Examples of such metal precursors are, for example, Rh (CO)2(acac)，[Rh(COD)2(OTf)]，[Rh(COD)Cl]2，[Rh(NBD)(acac)]Purchased from Sigma-Aldrich.
Further, the water-soluble ligand includes, but is not limited to, water-soluble bisphosphine ligand, monophosphine ligand, phosphorous acid ligand, phosphite ligand, nitrogen phosphorus ligand, diamine ligand, carbene ligand, and the like, preferably 5,5 '-phospho-R-BINAP, 5' -sodium sulfonate-R-BINAP, sulfonate-R, R-chiralphos, sulfonate-R, R-DPCP, sodium 4- ((2-amino-1, 2-diphenylethyl) sulfamoyl) benzenesulfonate, sodium 4- ((2-aminocyclohexyl) sulfamoyl) benzenesulfonate, sodium 4- ((2-amino-2-phenylethyl) sulfamoyl) benzenesulfonate.
The catalyst of the invention can be recycled for many times.
Further, the water-oil two-phase system (isomerization reaction system) is composed of water and oil phases, wherein the oil phase is a raw material phase or a product phase, the water phase is a catalyst phase, and the amount of water is 0.3-3.0 times, preferably 0.5-1.0 times of the mass of the raw material.
Further, the water-soluble metal complex is prepared in situ in the reactor from a metal precursor and a water-soluble ligand.
Further, the ratio of the metal precursor to the ligand is 1.0:0.5 to 10.0, preferably 1.0:1.01 to 5.0, more preferably about 1.0:1.1 to 2.0, and the preparation method is as follows: mixing the metal precursor, the water-soluble ligand and the solvent and optional lithium salt, for example, stirring and coordinating at room temperature for more than 10 minutes, and obtaining a complex solution after the metal precursor and the ligand are completely dissolved; wherein the solvent is preferably selected from tetrahydrofuran, methanol, ethanol, isopropanol, N-dimethylformamide and other organic solvents with good water solubility.
Further, the amount of the metal catalyst is 0.005-1 mol%, preferably 0.01-0.5 mol%, and more preferably 0.06-0.42 mol% of the molar amount of neral or geranial.
In a preferred embodiment, the catalyst further comprises a lithium salt, and the amount of the lithium salt is 1.0 to 4.0 times, preferably 2.0 to 3.0 times, the molar amount of the metal precursor. The metal is preferably rhodium metal. The lithium ion has stronger Lewis acid acidity, can coordinate with carbonyl, and improves the hydrogenation reaction selectivity. The lithium salt is selected from one or more of lithium chloride, lithium bromide, lithium acetate, lithium trifluoromethanesulfonate, etc.
In the invention, the pressure of the hydrogen is 1.0-10.0 MPa, preferably 6.0-8.0 MPa, and/or the reaction temperature is 40-120 ℃, preferably 70-80 ℃, and the reaction time is 6-12 hours, preferably 6-8 hours.
In the invention, after the reaction is finished, the reaction solution is cooled to room temperature, then the reaction solution is kept stand for phase separation, so that the separation of a product and a water phase can be realized, and the water phase containing the catalyst can be reused for more than 5 times.
According to a second aspect of the present invention there is provided a catalyst comprising a metal precursor and a water-soluble ligand,
wherein the metal precursor has the formula [ M (X) Y]Wherein M represents a metal ion including, but not limited to, ruthenium, rhodium, iridium, nickel, palladium, platinum, osmium, manganese, cobalt, iron, and the like, preferably rhodium metal; x represents a coordinating group including, but not limited to, ethylene, 1, 4-cyclooctadiene, norbornadiene, p-cymene, carbon monoxide, and the like, preferably carbon monoxide, 1, 4-cyclooctadiene, and norbornadiene; y represents an anion, including but not limited toFluorine, chlorine, bromine, iodine, trifluoromethanesulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, methoxide, acetylacetone, acetate, and the like. Examples of such metal precursors are, for example, Rh (CO)2(acac)，[Rh(COD)2(OTf)]，[Rh(COD)Cl]2，[Rh(NBD)(acac)]Purchased from Sigma-Aldrich.
Further, the water-soluble ligand includes, but is not limited to, water-soluble bisphosphine ligand, monophosphine ligand, phosphorous acid ligand, phosphite ligand, nitrogen phosphorus ligand, diamine ligand, carbene ligand, and the like, preferably 5,5 '-phospho-R-BINAP, 5' -sodium sulfonate-R-BINAP, sulfonate-R, R-chiralphos, sulfonate-R, R-DPCP, sodium 4- ((2-amino-1, 2-diphenylethyl) sulfamoyl) benzenesulfonate, sodium 4- ((2-aminocyclohexyl) sulfamoyl) benzenesulfonate, sodium 4- ((2-amino-2-phenylethyl) sulfamoyl) benzenesulfonate.
Further, the catalyst also comprises a lithium salt, and the dosage of the lithium salt is 2.0 to 4.0 times of the molar quantity of the metal precursor, and preferably 2.0 to 3.0 times. The metal is preferably rhodium metal. The lithium salt is selected from one or more of lithium chloride, lithium bromide, lithium acetate, lithium trifluoromethanesulfonate, etc.
According to a third aspect of the present invention, there is provided a method for producing the above catalyst, comprising: the metal precursor, the water-soluble ligand and the solvent are mixed, and the molar ratio of the metal precursor to the water-soluble ligand is 1.0:0.5 to 10.0, preferably 1.0:1.01 to 5.0, and more preferably about 1.0:1.1 to 2.0. Wherein the solvent is preferably selected from tetrahydrofuran, methanol, ethanol, isopropanol, N-dimethylformamide and other organic solvents with good water solubility. The amount of the solvent used is, for example, 2 to 50 times, preferably 5 to 20 times the total mass of the metal precursor and the water-soluble ligand.
Further, the method further comprises adding a lithium salt, wherein the amount of the lithium salt is 1.0-4.0 times, preferably 2.0-3.0 times of the molar amount of the metal precursor. The metal is preferably rhodium metal.
By adopting the technical scheme, the invention has the following positive effects:
1. the water-soluble ligand is used, so that the catalyst is low in consumption and can be recycled, and the catalyst cost is greatly reduced;
2. the catalyst is prepared by rhodium metal precursor and water-soluble phosphine ligand in situ, the process is simple, the operation is convenient, and the method is suitable for large-scale production;
3. the addition of lithium salt in the reaction system can accelerate the reaction and improve the stereoselectivity. The obtained chiral citronellal product has high yield and good stereoselectivity.
Detailed Description
The present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.
The main raw material information is as follows:
neral and geranial, 99.5% (GC), self-made;
tetrahydrofuran, Chinese medicine reagent and chromatographic purity;
Rh(CO)2(acac)，[Rh(COD)2(OTf)]，[Rh(COD)Cl]2，[Rh(NBD)(acac)]Sigma-Aldrich, 99%; sulfonated-R, R-chiralphos, 4,4 '-sodium phosphate-BINAP, 5,5' -sodium sulfonate-BINAP, (1R,2R) -4- ((2-aminocyclohexyl) sulfonamide) sodium benzenesulfonate, sulfonated-R, R-DPCP, synnaonoceae, 98%;
lithium chloride, lithium bromide, lithium acetate, lithium trifluoromethanesulfonate and an avadin reagent, wherein the percentage of the total weight of the solution is 99%.
The gas chromatography test conditions of the present invention are as follows:
the instrument model is Agilent GC, the chromatographic column is Agilent Supelco β -DEX 225(30m is multiplied by 0.25mm is multiplied by 0.25 mu m), the column temperature is 60 ℃, the temperature is increased to 80 ℃ at 5 ℃/min, then the temperature is increased to 150 ℃ at 10 ℃/min, finally the temperature is increased to 210 ℃ at 15 ℃/min, the temperature is kept for 5min, the injection port temperature is 280 ℃, the FID detector temperature is 300 ℃, the split injection is carried out, the split ratio is 60:1, the injection amount is 2.0 mu L, H2Flow rate: 40 mL/min; air flow rate: 400 mL/min.
Example 1
Catalyst preparation in a glove box, a metal precursor [ Rh (CO) ] was added sequentially to a single-neck flask equipped with a magnetic stirrer2(acac)](26.1mg,0.10mmol), sulfonated-R, R-DPCP (3,3' - (((1R,2R) -cyclobutane-1, 2-diylbis (methylene)) bis (phosphinotriyl)) sodium tetraphenylsulfonate) (91.9mg,0.11mmol) Starting stirring, promoting the dissolution of a metal precursor and a ligand, stirring and coordinating for 20 minutes to obtain a catalyst solution, sealing a single-mouth bottle by using a rubber plug, taking out of a glove box, and protecting by using a nitrogen balloon for later use.
Synthesis of R-citronellal by asymmetric hydrogenation of neral
The 250mL autoclave was sealed, pressure maintained, and after no problem was detected by leak detection, the autoclave was replaced with nitrogen 3 times. Addition was made by first feeding deoxygenated deionized water (10.0g,10.0mL) into the reactor using an advection pump, followed by the previously prepared catalyst solution, starting the autoclave with stirring, and finally adding the substrate neral (30.754g,0.2 mol). After the substrate is added, replacing nitrogen by hydrogen for three times, wherein each time is 2.0MPa, finally filling 6.0MPa hydrogen, starting the autoclave for heat tracing, starting timing when the temperature in the autoclave reaches 80 ℃, keeping the temperature for reaction for 6 hours, sampling and analyzing at regular time, detecting by GC, and determining the yield by an internal standard method, wherein the result shows that the yield of citronellal is 99.6 percent, and the ee value is 94.2 percent (R isomer is main).
Example 2
Preparation of the catalyst
In a glove box, a metal precursor [ Rh (CO) ] was added to a single-neck flask equipped with a magnetic stirrer in sequence2(acac)](140.3mg,0.40mmol), sulfonated-R, R-DPCP (3,3' - (((1R,2R) -cyclobutane-1, 2-diylbis (methylene)) bis (phosphinotriyl)) sodium tetraphenylsulfonate) (382.5mg,0.44mmol), lithium chloride (42.8mg,1.0mmol) and tetrahydrofuran (8.0mL), stirring was started to promote dissolution of the metal precursor and ligand, and after 20 minutes of coordination by stirring, a catalyst solution was obtained, a single-neck flask was sealed with a rubber stopper, taken out of a glove box and protected with a nitrogen balloon for use.
Synthesis of R-citronellal by asymmetric hydrogenation of neral
The 250mL autoclave was sealed, pressure maintained, and after no problem was detected by leak detection, the autoclave was replaced with nitrogen 3 times. Addition was made by first feeding deoxygenated deionized water (20.0g,20.0mL) into the reactor using an advection pump, followed by the previously prepared catalyst solution, starting the autoclave with stirring, and finally adding the substrate neral (30.754g,0.2 mol). After the substrate is added, replacing nitrogen by hydrogen for three times, wherein each time is 2.0MPa, finally filling 10.0MPa hydrogen, starting the autoclave for heat tracing, starting timing when the temperature in the autoclave reaches 40 ℃, keeping the temperature for reaction for 12 hours, sampling and analyzing at regular time, detecting by GC, and determining the yield by an internal standard method, wherein the result shows that the yield of citronellal is 99.8 percent, and the ee value is 94.3 percent (R isomer is main).
Example 3
Preparation of the catalyst
In a glove box, a metal precursor [ Rh (CO) ] was added to a single-neck flask equipped with a magnetic stirrer in sequence2(acac)](52.1mg,0.20mmol), sulfonated-R, R-DPCP (3,3' - (((1R,2R) -cyclobutane-1, 2-diylbis (methylene)) bis (phosphinotriyl)) sodium tetraphenylsulfonate) (191.3mg,0.22mmol), lithium chloride (25.7mg,0.60mmol) and tetrahydrofuran (4.0mL), stirring was turned on to promote dissolution of the metal precursor and ligand, and after 20 minutes of coordination by stirring, a catalyst solution was obtained, a single vial was sealed with a rubber stopper, taken out of a glove box and protected with a nitrogen balloon for use.
Synthesis of R-citronellal by asymmetric hydrogenation of neral
The 250mL autoclave was sealed, pressure maintained, and after no problem was detected by leak detection, the autoclave was replaced with nitrogen 3 times. Addition was made by first feeding deoxygenated deionized water (20.0g,20.0mL) into the reactor using an advection pump, followed by the previously prepared catalyst solution, starting the autoclave with stirring, and finally adding the substrate neral (30.754g,0.2 mol). After the substrate is added, replacing nitrogen by hydrogen for three times, each time is 2.0MPa, finally filling 3.0MPa hydrogen, starting the autoclave for heat tracing, starting timing when the temperature in the autoclave reaches 100 ℃, keeping the temperature for reaction for 6 hours, sampling and analyzing at regular time, carrying out GC (gas chromatography) detection, and determining the yield by an internal standard method, wherein the result shows that the yield of the citronellal is 99.1 percent, and the ee value is 92.4 percent (the R isomer is main).
Example 4
Preparation of the catalyst
In a glove box, a metal precursor [ Rh (CO) ] was added to a single-neck flask equipped with a magnetic stirrer in sequence2(acac)](5.2mg,0.02mmol), sulfonated-R, R-DPCP (3,3' - (((1R,2R) -cyclobutane-1, 2-diylbis (methylene)) bis (phosphinotriyl)) sodium tetraphenylsulfonate) (19.1mg,0.022mmol) and tetrahydrofuran (1.0mL), stirring was turned on,promoting the dissolution of the metal precursor and the ligand, stirring and coordinating for 20 minutes to obtain a catalyst solution, sealing the single-mouth bottle by using a rubber plug, discharging from a glove box, and protecting by using a nitrogen balloon for later use.
Asymmetrically hydrogenating neral to synthesize R-citronellal without adding lithium salt
The 250mL autoclave was sealed, pressure maintained, and after no problem was detected by leak detection, the autoclave was replaced with nitrogen 3 times. Addition was made by first feeding deoxygenated deionized water (30.7g,30.7mL) into the reactor using an advection pump, followed by the previously prepared catalyst solution, starting the autoclave with stirring, and finally adding the substrate neral (30.754g,0.2 mol). After the substrate is added, replacing nitrogen by hydrogen for three times, wherein each time is 2.0MPa, finally filling 3.0MPa hydrogen, starting the autoclave for heat tracing, starting timing when the temperature in the autoclave reaches 100 ℃, keeping the temperature for 10 hours, sampling and analyzing at regular time, carrying out GC (gas chromatography) detection, and determining the yield by an internal standard method, wherein the result shows that the yield of the citronellal is 80.2 percent, and the ee value is 88.5 percent (the R isomer is main).
Example 5
Preparation of the catalyst
In a glove box, a metal precursor [ Rh (CO) ] was added to a single-neck flask equipped with a magnetic stirrer in sequence2(acac)](26.1mg,0.10mmol), sulfonated-R, R-chiralPhos (3,3' - ((2R,3R) -2, 3-dimethylbutane-1, 4-diyl) bis (phosphinotriyl)) sodium tetraphenylsulfonate) (113.3mg,0.13mmol), lithium chloride (12.8mg,0.30mmol) and tetrahydrofuran (4.0mL) were started to stir, to promote dissolution of the metal precursor and ligand, to obtain a catalyst solution after 20 minutes of coordination by stirring, and a single vial was sealed with a rubber stopper, taken out of the glove box and protected with a nitrogen balloon for future use.
Synthesis of R-citronellal by asymmetric hydrogenation of neral
The 250mL autoclave was sealed, pressure maintained, and after no problem was detected by leak detection, the autoclave was replaced with nitrogen 3 times. Addition was made by first feeding deoxygenated deionized water (10.0g,10.0mL) into the reactor using an advection pump, followed by the previously prepared catalyst solution, starting the autoclave with stirring, and finally adding the substrate neral (30.754g,0.2 mol). After the substrate is added, replacing nitrogen by hydrogen for three times, each time is 2.0MPa, finally filling 6.0MPa hydrogen, starting the autoclave for heat tracing, starting timing when the temperature in the autoclave reaches 70 ℃, keeping the temperature for reaction for 6 hours, sampling and analyzing at regular time, carrying out GC (gas chromatography) detection, and determining the yield by an internal standard method, wherein the result shows that the yield of the citronellal is 99.6 percent, and the ee value is 96.1 percent (the R isomer is main).
Example 6
Preparation of the catalyst
In the glove box, a metal precursor [ rh (nbd) (acac)) (29.7mg,0.10mmol), 4 '-sodium phosphate-BINAP ((2,2' -bis (diphenylphosphino) - [1,1 '-binaphthyl ] -4,4' -diyl) bis (sodium phosphonate)) (131.9mg,0.15mmol), lithium bromide (26.3mg,0.30mmol) and ethanol (6.0mL) were added in this order to a single-neck flask equipped with a magnetic stirrer, stirring was started to promote dissolution of the metal precursor and the ligand, and after 20 minutes of coordination by stirring, a catalyst solution was obtained, the single-neck flask was sealed with a rubber stopper, taken out of the glove box, and protected with a nitrogen balloon for future use.
Synthesis of R-citronellal by asymmetric hydrogenation of neral
The 250mL autoclave was sealed, pressure maintained, and after no problem was detected by leak detection, the autoclave was replaced with nitrogen 3 times. Addition was made by first feeding deoxygenated deionized water (10.0g,10.0mL) into the reactor using an advection pump, followed by the previously prepared catalyst solution, starting the autoclave with stirring, and finally adding the substrate neral (30.754g,0.2 mol). After the substrate is added, replacing nitrogen by hydrogen for three times, each time is 2.0MPa, finally filling 6.0MPa hydrogen, starting the autoclave for heat tracing, starting timing when the temperature in the autoclave reaches 80 ℃, keeping the temperature for reaction for 6 hours, sampling and analyzing at regular time, detecting by GC, determining the yield by an internal standard method, and the result shows that the yield of citronellal is 95.5 percent and the ee value is 90.5 percent (R isomer is main).
Example 7
Preparation of the catalyst
In a glove box, a metal precursor [ Rh (COD) Cl ] was added to a single-neck flask equipped with a magnetic stirrer in sequence]2(49.8mg,0.10mmol), 5' -sodium sulfonate-BINAP ((2,2' -bis (diphenylphosphino) - [1,1' -binaphthyl) -)]-5,5' -diyl) sodium sulfonate) (167.0mg,0.20mmol), lithium acetate (20.0mg,0.30mmol) and N, N-dimethylformamide (4.0mL), stirring was turned on to promote dissolution of the metal precursor and ligand, and after stirring for 20 minutes of coordination, catalysis was obtainedSealing the single-mouth bottle with a rubber plug, discharging the solution out of the glove box, and protecting the solution with a nitrogen balloon for later use.
Synthesis of R-citronellal by asymmetric hydrogenation of neral
The 250mL autoclave was sealed, pressure maintained, and after no problem was detected by leak detection, the autoclave was replaced with nitrogen 3 times. Addition was made by first feeding deoxygenated deionized water (10.0g,10.0mL) into the reactor using an advection pump, followed by the previously prepared catalyst solution, starting the autoclave with stirring, and finally adding the substrate neral (30.754g,0.2 mol). After the substrate is added, replacing nitrogen by hydrogen for three times, wherein each time is 2.0MPa, finally filling 6.0MPa hydrogen, starting the autoclave for heat tracing, starting timing when the temperature in the autoclave reaches 80 ℃, keeping the temperature for reaction for 8 hours, sampling and analyzing at regular time, detecting by GC, determining the yield by an internal standard method, and the result shows that the yield of the citronellal is 96.5 percent and the ee value is 91.2 percent (the R isomer is main).
Example 8
Preparation of the catalyst
In a glove box, a metal precursor [ Rh (COD) ] was added to a single-neck flask equipped with a magnetic stirrer in sequence2OTf](9.5mg,0.10mmol), (1R,2R) -4- ((2-aminocyclohexyl) sulfamoyl) benzenesulfonic acid sodium salt 4- (N- ((1R,2R) -2-aminocyclohexyl) sulfamoyl) benzanesulfonic acid) (40.36mg,0.12mmol), lithium trifluoromethanesulfonate (31.67mg,0.2mmol) and tetrahydrofuran (1.0mL), stirring was started to promote dissolution of the metal precursor and the ligand, and after stirring and coordination for 20 minutes, a catalyst solution was obtained, and a single vial was sealed with a rubber stopper, taken out of a glove box and protected with a nitrogen balloon for use.
Synthesis of R-citronellal by asymmetric hydrogenation of neral
The 250mL autoclave was sealed, pressure maintained, and after no problem was detected by leak detection, the autoclave was replaced with nitrogen 3 times. Addition was made by first feeding deoxygenated deionized water (10.0g,10.0mL) into the reactor using an advection pump, followed by the previously prepared catalyst solution, starting the autoclave with stirring, and finally adding the substrate neral (30.754g,0.2 mol). After the substrate is added, replacing nitrogen by hydrogen for three times, each time is 2.0MPa, finally filling 6.0MPa hydrogen, starting the autoclave for heat tracing, starting timing when the temperature in the autoclave reaches 80 ℃, keeping the temperature for reaction for 8 hours, sampling and analyzing at regular time, detecting by GC, determining the yield by an internal standard method, and the result shows that the yield of the citronellal is 99.1 percent and the ee value is 95.1 percent (the R isomer is main).
Example 9
Preparation of the catalyst
In a glove box, a metal precursor [ Rh (CO) ] was added to a single-neck flask equipped with a magnetic stirrer in sequence2(acac)](26.1mg,0.10mmol), sulfonated-S, S-chiralPhos (3,3' - ((2S,3S) -2, 3-dimethylbutane-1, 4-diyl) bis (phosphinotriyl)) sodium tetraphenylsulfonate) (113.3mg,0.13mmol), lithium chloride (12.8mg,0.30mmol) and tetrahydrofuran (3.0mL), stirring was started to promote dissolution of the metal precursor and ligand, and after 20 minutes of coordination by stirring, a catalyst solution was obtained, a single vial was sealed with a rubber stopper, taken out of the glove box and protected with a nitrogen balloon for future use.
Synthesis of R-citronellal by asymmetric hydrogenation of geranial
The 250mL autoclave was sealed, pressure maintained, and after no problem was detected by leak detection, the autoclave was replaced with nitrogen 3 times. Addition was made by first feeding deoxygenated deionized water (10.0g,10.0mL) into the reactor using an advection pump, followed by the previously prepared catalyst solution, starting the autoclave with stirring, and finally adding the substrate neral (30.754g,0.2 mol). After the substrate is added, replacing nitrogen by hydrogen for three times, each time is 2.0MPa, finally filling 7.0MPa hydrogen, starting the autoclave for heat tracing, starting timing when the temperature in the autoclave reaches 80 ℃, keeping the temperature for reaction for 8 hours, sampling and analyzing at regular time, carrying out GC (gas chromatography) detection, and determining the yield by an internal standard method, wherein the result shows that the yield of the citronellal is 99.8 percent, and the ee value is 96.7 percent (the R isomer is main).
Comparative example 1
Asymmetric hydrogenation of cis-citral in the presence of carbon monoxide (patent CN101932543)
Under a protective gas atmosphere, 17.9mg of Rh (CO)2acac and 38.5mg of (R, R) -chiralphos were dissolved in 20g of toluene and transferred to a 100ml autoclave which had been flushed 3 times beforehand with a mixture of carbon monoxide and hydrogen (1:1, vol/vol). The mixture is mixed in 1:1CO/H2The mixture was stirred at 60 ℃ for 3 hours under 8 bar and then cooled to room temperature. Then 15 bar H by means of a pressure lock2Injecting 10.94g of orange flowerAldehyde (neral/geranial double bond isomer ratio 99.1: 0.9; substrate/catalyst ratio 1000). The reaction pressure was adjusted to 80 bar by injecting hydrogen. To reduce the CO partial pressure, the pressure was reduced 3 times and after a further 3 hours again to 8 bar, and then brought back to 80 bar by injecting hydrogen. After 18 hours, the conversion was 99.9% and the yield of D-citronellal was 99.8%, as determined by gas chromatography, with an optical purity of 90% ee.
Examples 10 to 14
Preparation of the catalyst
In a glove box, a metal precursor [ Rh (CO) ] was added to a single-neck flask equipped with a magnetic stirrer in sequence2(acac)](10.4mg,0.04mmol), sulfonated-R, R-chiralPhos (3,3' - ((2R,3R) -2, 3-dimethylbutane-1, 4-diyl) bis (phosphinotriyl)) sodium tetraphenylsulfonate) (69.7mg,0.08mmol), lithium chloride (5.1mg,0.12mmol) and tetrahydrofuran (2.0mL) were started to stir, to promote dissolution of the metal precursor and ligand, to obtain a catalyst solution after 20 minutes of coordination by stirring, and a single-neck flask was sealed with a rubber stopper, taken out of a glove box, and protected with a nitrogen balloon for future use.
Experiment for synthesizing R-citronellal by asymmetrically hydrogenating neral and mechanically applying catalyst
The 250mL autoclave was sealed, pressure maintained, and after no problem was detected by leak detection, the autoclave was replaced with nitrogen 3 times. Addition was made by first feeding deoxygenated deionized water (10.0g,10.0mL) into the reactor using an advection pump, followed by the previously prepared catalyst solution, starting the autoclave with stirring, and finally adding the substrate neral (30.754g,0.2 mol). And (3) after adding the substrate, replacing nitrogen by hydrogen for three times with 2.0MPa each time, finally filling 8.0MPa hydrogen, starting the autoclave for heat tracing, starting timing when the temperature in the autoclave reaches 80 ℃, carrying out heat preservation reaction for 6-10 hours, sampling and analyzing at regular time, carrying out GC detection, and determining the yield by an internal standard method.
Releasing high-pressure hydrogen in the reaction kettle, replacing the nitrogen for 3 times, keeping the micro-positive pressure in the kettle, pressing the oil phase out of the reaction kettle carefully through a bottom inserting pipe, remaining the water phase in the kettle, and detecting the yield and the ee value of the citronellal by GC. And (2) adding a substrate neral (30.754g,0.2mol) into the autoclave again, replacing nitrogen with hydrogen for three times, wherein each time is 2.0MPa, finally filling 8.0MPa of hydrogen, starting heating, raising the internal temperature of the reaction kettle to 80 ℃, keeping the temperature constant, and repeating the operation after keeping the temperature for 6-10 hours. The catalyst in the water phase can be recycled for more than 5 times, and the specific reaction results are shown in the following table.
Examples 10 to 14 reaction results
Figure BDA0002305152980000101

Claims (10)

1. A process for the asymmetric hydrogenation of R-citronellal in a two-phase water-oil phase, comprising: hydrogen is used as a reducing agent, a water-soluble metal complex is used as a catalyst, and neral or geranial is asymmetrically hydrogenated in a water-oil two-phase system to obtain R-citronellal; after the reaction is finished, separating citronellal and the catalyst by oil-water split-phase separation;
the water-soluble metal complex comprises a metal precursor and a water-soluble ligand,
wherein the metal precursor has the formula [ M (X) Y ], wherein M represents a metal ion, preferably selected from ruthenium, rhodium, iridium, nickel, palladium, platinum, osmium, manganese, cobalt, iron, more preferably rhodium metal;
x represents a coordinating group, preferably selected from ethylene, 1, 4-cyclooctadiene, norbornadiene, p-cymene, carbon monoxide, preferably carbon monoxide, 1, 4-cyclooctadiene and norbornadiene;
y represents an anion, preferably selected from fluorine, chlorine, bromine, iodine, trifluoromethanesulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, methoxy, acetylacetone, acetate.
2. The method of claim 1, wherein the metal precursor is selected from Rh (CO)2(acac)，[Rh(COD)2(OTf)]，[Rh(COD)Cl]2，[Rh(NBD)(acac)](ii) a And/or
The water-soluble ligand is selected from the group consisting of water-soluble bisphosphine ligands, monophosphine ligands, phosphorous acid ligands, phosphite ligands, nitrogen phosphorus ligands, diamine ligands, carbene ligands, preferably 5,5 '-phospho-R-BINAP, 5' -sodium sulfonate-R-BINAP, sulfonate-R, R-ChiraPhos, sulfonate-R, R-DPCP, sodium 4- ((2-amino-1, 2-diphenylethyl) sulfamoyl) benzenesulfonate, sodium 4- ((2-aminocyclohexyl) sulfamoyl) benzenesulfonate, sodium 4- ((2-amino-2-phenylethyl) sulfamoyl) benzenesulfonate.
3. The method according to claim 1 or 2, wherein the water-oil two-phase system consists of water-oil two phases, wherein the oil phase is a raw material phase or a product phase, the water phase is a catalyst phase, and the amount of water is 0.3-3.0 times, preferably 0.5-1.0 times of the mass of the raw material.
4. A process according to any one of claims 1 to 3, wherein the molar ratio of metal precursor to ligand is from 1.0:0.5 to 10.0, preferably from 1.0:1.01 to 5.0, more preferably from about 1.0:1.1 to 2.0.
5. The method according to any one of claims 1 to 4, wherein the metal complex catalyst is used in an amount of 0.01 to 0.5 mol%, preferably 0.06 to 0.42 mol%, based on the molar amount of neral or geranial.
6. The process according to any one of claims 1 to 5, wherein the catalyst further comprises a lithium salt in an amount of 1.0 to 4.0 times, preferably 2.0 to 3.0 times, the molar amount of the metal precursor.
7. The process according to any one of claims 1 to 6, wherein the pressure of the hydrogen is 1.0 to 10.0MPa, preferably 6.0 to 8.0MPa, and/or the reaction temperature is 40 to 120 ℃, preferably 70 to 80 ℃, and the reaction time is 6 to 12 hours, preferably 6 to 8 hours.
8. A catalyst comprising a metal precursor and a water-soluble ligand,
wherein the metal precursor has the formula [ M (X) Y ], wherein M represents a metal ion, preferably selected from ruthenium, rhodium, iridium, nickel, palladium, platinum, osmium, manganese, cobalt, iron, more preferably rhodium metal;
x represents a coordinating group, preferably selected from ethylene, 1, 4-cyclooctadiene, norbornadiene, p-cymene, carbon monoxide, more preferably carbon monoxide, 1, 4-cyclooctadiene or norbornadiene;
y represents an anion, preferably selected from fluorine, chlorine, bromine, iodine, trifluoromethanesulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, methoxy, acetylacetone, acetate;
preferably, the water-soluble ligand is selected from the group consisting of water-soluble bisphosphine ligands, monophosphine ligands, phosphorous acid ligands, phosphite ligands, nitrogen phosphorus ligands, diamine ligands, carbene ligands, more preferably from the group consisting of 5,5 '-phospho-R-BINAP, 5' -sodium sulfonate-R-BINAP, sulfonate-R, R-chiralphos, sulfonate-R, R-DPCP, sodium 4- ((2-amino-1, 2-diphenylethyl) sulfamoyl) benzenesulfonate, sodium 4- ((2-aminocyclohexyl) sulfamoyl) benzenesulfonate, sodium 4- ((2-amino-2-phenylethyl) sulfamoyl) benzenesulfonate.
9. The catalyst according to claim 8, wherein the catalyst further comprises a lithium salt in an amount of 1.0 to 4.0 times, preferably 2.0 to 3.0 times, the molar amount of the metal precursor.
10. A method of preparing a catalyst according to claim 8 or 9, the method comprising: mixing a metal precursor, a water-soluble ligand and a solvent, wherein the molar ratio of the metal precursor to the water-soluble ligand is 1.0: 0.5-10.0, preferably 1.0:1.01-5.0, and more preferably about 1.0: 1.1-2.0;
preferably, the solvent used is selected from tetrahydrofuran, methanol, ethanol, isopropanol, N-dimethylformamide; and/or
The amount of the solvent to be used is, for example, 2 to 50 times, preferably 5 to 20 times, the total mass of the metal precursor and the water-soluble ligand; and/or
The method further comprises adding a lithium salt, wherein the amount of the lithium salt is 1.0-4.0 times, preferably 2.0-3.0 times of the molar amount of the metal precursor.
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