CN112110805B - Method for preparing R-citronellal - Google Patents
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- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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Abstract
The invention provides a method for preparing R-citronellal, which comprises the following steps: neral, geranial or a mixture of the neral and the geranial are subjected to asymmetric hydrogenation reaction in the presence of a transition metal catalyst to generate R-citronellal, a two-stage nanofiltration membrane separation system is adopted to separate the catalyst in the reaction liquid and purify the reaction raw materials of the next batch, and the obtained filtrate is directly subjected to the reaction of the next batch. The method can obviously improve the catalytic activity and the mechanical stability of the high-level catalyst, thereby realizing higher cumulative conversion number.
Description
Technical Field
The invention belongs to the field of spice synthesis, and particularly relates to a method for preparing R-citronellal.
Technical Field
Citronellal (3, 7-dimethyl-6-octenal), a chain acyclic monoterpene aldehyde, is naturally present in essential oils such as lemon oil and citronella oil. Citronellal as a spice raw material can be used for preparing edible essences, citrus and cherry flavors, is also an important raw material for synthesizing citronellol, hydroxycitronellal, menthol and the like, and has important application value in the field of spices and organic synthesis industry.
There are two major pathways for citronellal to be derived. Firstly, the extract can be obtained from citronella oil through extraction; secondly, the organic compound is obtained by organic synthesis industry: citronellal can be prepared by oxidation or catalytic dehydrogenation of citronellol, or can be obtained by catalytic hydrogenation of citral. Because of the asymmetric carbon atom in the citronellal molecule, people have been concerned about obtaining natural equivalent optical activity citronellal by asymmetric catalysis technology.
CN101039894 discloses a method for preparing optically active citronellal by asymmetrically hydrogenating neral or geranial, using a catalyst composed of an expensive noble metal and a chiral ligand. After the reaction is finished, the catalyst is separated from the product by a distillation method, the recovered catalyst can be recycled only by prefabrication in the presence of high-pressure synthesis gas, and the method has the defects of complex process operation, high risk and the like.
CN 110963902 discloses a method for synthesizing R-citronellal by water-oil two-phase asymmetric hydrogenation, which enables a catalyst to have good water solubility by using a water-soluble phosphine ligand, and realizes separation of the catalyst by phase separation after the reaction is finished.
CN 110981707 discloses a method for isomerizing and synthesizing chiral citronellal by nerol or geraniol under the combined action of a metal catalyst and alkali, and the method also adopts a water-soluble ligand to realize two-phase catalysis and separate citronellal and the catalyst by oil-water phase separation.
Although the method adopting the water-soluble ligand can separate and apply the catalyst mechanically through oil-water phase separation, the liquid-gas three-phase reaction has the defect of low mass transfer efficiency, so that the space-time yield is difficult to satisfy during industrial scale production.
In order to reduce the production cost of optically active R-citronellal, the development of an efficient method for preparing R-citronellal by asymmetric hydrogenation of citral is urgently needed at present, the activity and stability of a catalyst are improved, the catalyst is efficiently separated from a reaction system at low cost and is applied mechanically in multiple batches, and a high accumulated conversion number is realized, so that the cost of the catalyst is reduced, and the economic benefit is improved.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing R-citronellal by asymmetrically hydrogenating neral and/or geranial.
The inventor of the application surprisingly finds that after the hydrogenation reaction is finished, the TFC type nanofiltration membrane is used for filtering and concentrating the catalyst in the reaction liquid, so that the catalyst concentrated solution and the product R-citronellal can be efficiently obtained; and adding the neral and/or geranial serving as the reaction raw materials of the next batch into the concentrated catalyst solution, and filtering by using an ISA type nanofiltration membrane to obtain a mixture of the purified reaction raw materials and the catalyst, wherein the reaction of the next batch can be directly carried out. By filtering through the two-stage nanofiltration membrane, the catalyst is applied mechanically, and reaction raw materials are purified simultaneously, so that the activity and stability of the applied catalyst are obviously improved, and a higher cumulative conversion number is realized.
In order to achieve the above purpose, the invention adopts the following technical scheme:
s1: reaction substrates, namely neral of formula (I) and/or geranial of formula (II) are subjected to asymmetric hydrogenation reaction in the presence of a catalyst to generate R-citronellal of formula (III);
s2: performing primary nanofiltration separation on the S1 reaction liquid by using a nanofiltration membrane M to obtain a catalyst concentrated solution and a dialysate containing a product R-citronellal, and separating the dialysate to obtain a reaction product citronellal without a catalyst;
s3: and adding the next batch of reaction raw materials into the concentrated catalyst solution of S2, performing secondary nanofiltration separation by using a nanofiltration membrane N to obtain dialysate containing a mixture of the purified reaction raw materials and the catalyst, directly performing the next batch of reaction on the mixture, and separating the dialysate to recover the catalyst.
In the present invention, the reaction substrate may be neral or geranial, or may be a mixture of neral and geranial, and for the mixture of neral and geranial, the ratio conventionally used in the art for preparing R-citronellal may be adopted. Preferred reaction substrates are neral reaction substrates having a neral/geranial molar ratio of at least 90:10, or geranial reaction substrates having a geranial/neral molar ratio of at least 90: 10. As is well known in the art, the optical purity of the obtained active citronellal depends on the ratio of neral to geranial in the raw material, the type and purity of the chiral ligand, and the optical purity of the prepared active citronellal is preferably at least 70 ee%.
In the present invention, the specific selection of the transition metal compounds and complexes (optically active ligands containing two phosphorus atoms) may be those known in the art and well described in the literature or may be prepared by one skilled in the art analogously to compounds known in the art.
In the present invention, the optically active ligand containing two phosphorus atoms may employ those conventionally used in the art for preparing R-citronellal.
In the present invention, the catalyst in S1 is a transition metal catalyst, preferably obtained by reacting a transition metal compound soluble in the reaction system with an optically active ligand containing two phosphorus atoms; preferably, the molar ratio of the transition metal atom in the transition metal compound to the optically active ligand comprising two phosphorus atoms is (0.5-10): 1, preferably (0.5-1): 1.
in the present invention, the transition metal element in the transition metal compound in S1 is selected from metal elements of group VIII of the periodic table, and is preferably rhodium.
In the invention, the transition metal compound is one or more of transition metal halide, transition metal carbonate and transition metal complex; preferably, the transition metal complex is selected from complexes formed by coordination of transition metals and one or more of carbonyl compounds, acetylacetone compounds, hydroxyl compounds, cyclooctadiene, norbornadiene, cyclooctene, methoxy compounds, acetyl compounds, aliphatic carboxylic acid compounds or aromatic carboxylic acid compounds; further preferably, the transition metal compound is selected from one or more of a transition metal halide, a complex formed by coordination of a transition metal and a carbonyl compound, a complex formed by coordination of a transition metal and cyclooctadiene, and a complex formed by coordination of a transition metal and an acetyl compound; more preferably, the transition metal compound is selected from RhCl3、Rh(OAc)3、Rh(cod)2BF4、[Rh(cod)Cl]2、Rh(CO)2acac、[Rh(cod)OH]2、[Rh(cod)OMe]2、Rh4(CO)12And Rh6(CO)16Wherein "acac" is an acetylacetone ligand and "cod" is a cyclooctadiene ligand.
In the present invention, the optically active ligand containing two phosphorus atoms described in S1 is selected from one or more of the following ligands represented by the general formulae (iv) and (v):
wherein R is1、R2Each independently of the others, an unbranched alkyl radical having from 1 to 20 carbon atoms, a branched alkyl radical OR a cyclic alkyl radical, optionally bearing one OR more olefinic double bonds, and/OR, optionally, one OR more identical OR different radicals from the group OR9、NR10R11Halogen, C6-C10Aryl and C3-C9A substituent of heteroaryl; or R1And R2Taken together to form a ring having from 4 to 20 ring-forming carbon atoms, and
R3、R4each independently hydrogen or straight chain C1-C4Alkyl or branched C1-C4Alkyl, and
R5、R6、R7、R8each independently is C6-C10Aryl, and each may optionally bear one or more groups selected from C1-C4Alkyl radical, C6-C10Aryl radical, C1-C4Substituents of alkoxy and amino, and
R9、R10、R11each independently is hydrogen, C1-C4Alkyl radical, C6-C10Aryl radical, C7-C12Aralkyl or C7-C12Alkylaryl, or R10、R11Taken together to form an alkylene chain having 2 to 5 carbon atoms and optionally interrupted by an N atom or an O atom.
As an example, the optically active ligand containing two phosphorus atoms may employ one or more of a chiral bidentate diphosphine ligand having the following structural formula and enantiomers thereof:
wherein Ph denotes phenyl, Ph2Means that it is linked to PTwo phenyl groups of (a).
In the present invention, the asymmetric hydrogenation in S1 is carried out at an absolute pressure (that is, hydrogen pressure) of 10 to 100 bar, preferably 50 to 80 bar; the reaction temperature is from 0 to 120 ℃ and preferably from 25 to 90 ℃. The reaction time is not particularly limited and may be determined by one skilled in the art according to the reaction conditions, and for example, the reaction time may be about 1h to about 150h, preferably about 2h to about 24 h.
The amount of the transition metal compound is not particularly limited, and those conventionally used in the art may be used, as appropriate by those skilled in the art according to the reaction requirements. For example, in some embodiments, the transition metal compound may be suitably used in an amount of 0.000,1mol% to 0.1mol% based on the molar amount of the transition metal atom, based on the amount of the reaction substrate to be hydrogenated.
In the invention, the technical scheme for separating the reaction feed liquid is that a two-stage nanofiltration membrane separation system is adopted to concentrate the reacted feed liquid, a reaction product citronellal without a catalyst is separated from the dialysate separated by the first-stage nanofiltration, and the transition metal catalyst is separated and recovered from the dialysate separated by the second-stage nanofiltration.
The process for separating the citronellal and the transition metal catalyst from the reaction product mixed solution comprises the following steps:
(1) first-stage nanofiltration separation
And after the reaction is finished, the reaction liquid is cooled and then conveyed to a first-stage nanofiltration separation system, a TFC type organic solvent-resistant nanofiltration membrane is used for separation, the permeate liquid is a purified reaction product citronellal, and the permeate liquid which does not permeate the nanofiltration membrane is a catalyst concentrated solution. The purpose of the first stage nanofiltration in the invention is to separate the product citronellal, and the nanofiltration membrane M used in the first stage nanofiltration separation in S2 is a TFC type nanofiltration membrane, preferably a STARMEM series product KOCH MPF-60 from GRACE, more preferably STARMEM 228.
The concentration of the catalyst for the first-stage nanofiltration separation and filtration in S2 is 0.000,1mol% -0.1mol%, based on the total molar weight of the substrate, the temperature of the feed liquid is 10-40 ℃, the pH range of the feed liquid is 7.1-8.3, the filtration pressure is 5-50 bar absolute pressure, and the solution viscosity is less than 10cp (25 ℃).
(2) Two-stage nanofiltration separation
Adding the concentrated solution separated by the primary nanofiltration separation system into the next batch of neral and/or geranial raw materials, mixing completely, conveying to the secondary nanofiltration separation system, separating by using an ISA type organic solvent-resistant nanofiltration membrane, wherein the permeate liquid is a purified transition metal catalyst and a reaction raw material, the secondary nanofiltration aims at purifying the transition metal catalyst and the reaction raw material, and the nanofiltration membrane N used for the secondary nanofiltration separation in S3 is an ISA type nanofiltration membrane, preferably DM series products of winning companies or PM selected of winning companies, and more preferably DM 900.
The concentration of the second-stage nanofiltration separation and filtration catalyst in S3 is 0.000,1mol% -0.1mol%, based on the total molar weight of the substrate, the temperature of the feed liquid is 10-40 ℃, the pH range of the feed liquid is 6.5-7.8, the filtration pressure is 20-40 bar absolute pressure, and the solution viscosity is less than 10cp (25 ℃).
(3) Application of catalyst
Putting the transition metal catalyst obtained by the secondary nanofiltration and the reaction raw material permeate into the next batch of reaction, and obtaining the R-citronellal product under the same reaction conditions.
The nanofiltration membrane used in the invention can be a roll-type nanofiltration membrane, and can also be a hollow fiber nanofiltration membrane.
Based on the scheme of the invention, good optical purity and conversion rate of the product can be obtained, and in some preferred schemes, the optical purity of the product of asymmetric hydrogenation can reach more than 90ee percent, and the conversion rate can reach 99 percent.
Suitable reactors for carrying out the asymmetric hydrogenation of the invention are in principle all those vessels which allow reaction under the stated conditions, in particular pressure and temperature, and which are suitable for hydrogenation, for example autoclaves, tubular reactors, bubble columns, etc., without this being restricted in particular.
The process of the invention can be operated batchwise, semi-continuously or continuously and is particularly suitable for industrial scale production.
The invention realizes effective recycling of the catalyst through reasonable design of a filtration system and optimization of nanofiltration membrane type selection. After the reaction is finished, the reaction solution mainly comprises a product citronellal, a transition metal catalyst and a small amount of macromolecular substances (mainly citronellal polymers) generated in a reaction system. The first-stage nanofiltration membrane is selected from a TFC type organic solvent-resistant nanofiltration membrane, and the type of nanofiltration membrane is a multilayer composite membrane. The separation membrane layer has smaller thickness, so the separation membrane layer has higher flux, and can quickly separate small molecular substances, namely the product R-citronellal; due to the high retention rate of the product on multivalent ions, the product R-citronellal can permeate through the product with high selectivity, and a transition metal catalyst in a reaction liquid is intercepted. The concentrated solution which does not penetrate through the nanofiltration membrane contains citronellal, a transition metal catalyst, macromolecular substances generated in a reaction system and the like, so that the catalyst is concentrated. And adding the raw materials of the next batch into the concentrated catalyst solution, and then carrying out secondary nanofiltration purification. The second-stage nanofiltration membrane is selected to be an ISA type organic solvent resistant nanofiltration membrane which is an asymmetric membrane, and due to the high interception performance to macromolecules and the high selectivity to anions, the high-selectivity permeation of a transition metal catalyst, citronellal and the neral/geranial of the next batch of raw materials can be realized, and macromolecular substances generated in a reaction system, trace neral/geranial polymers in the neral/geranial of the raw materials and impurities containing heteroatoms such as sulfur and chlorine cannot permeate through the system, so that substances which have influences on the activity of the catalyst after being accumulated in the applying process are separated out of the system, a very good purification effect is achieved, and the activity and the stability of the applied catalyst are ensured.
Another object of the present invention is to provide a product of R-citronellal.
R-citronellal is prepared by the preparation method.
Compared with the prior art, the invention has the following positive effects:
the invention provides an improved method for preparing R-citronellal by asymmetric hydrogenation of neral and/or geranial under the catalysis of a transition metal catalyst, which realizes the application of the catalyst and obviously improves the activity and stability of the applied catalyst by filtering through a two-stage nanofiltration membrane, thereby realizing higher cumulative conversion number, wherein the cumulative conversion number of the preferred scheme can reach 19,600,000. Low cost is separated from the reaction system and multiple batches of catalyst are reused, thus reducing the cost of the catalyst and improving the economic benefit.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Analytical instrument
Gas chromatograph: agilent7890, column DB-5 (conversion assay), column Supelco beta-DEXTM225 (optical purity measurement), injection port temperature: 300 ℃; the split ratio is 50: 1; carrier gas flow rate: 52.8 ml/min; temperature rising procedure: at 95 ℃ for 40min, increasing to 180 ℃ at a rate of 10 ℃/min, for 40min, detector temperature: at a temperature of 280 ℃.
Device information:
a reaction kettle: 500mL autoclave, Nicoti Atsen mechanical science and technology, Inc.
And (3) a filtering system: laboratory membrane separation equipment WTM-1812G, huntington membrane engineering, inc.
Reagent:
raw material (neral): 99% of carbofuran.
Starting material (geranial): 99% of carbofuran.
RhCl3、Rh(OAc)3、Rh(cod)2BF4、Rh(CO)2acac、[Rh(cod)OH]2、Rh6(CO)16，Aldrich；
99 wt% of compound of formula (VI) -formula (XI) and carbofuran.
A nanofiltration membrane M:
nanofiltration membranes STARMEM228, Grace;
nanofiltration membrane MPF-60, KOCH company, MWCO (molecular weight cut off) 280, maximum pressure 60 bar, maximum temperature 50 ℃, optimum pH 7.
A nanofiltration membrane N:
nanofiltration membrane DM900, winning;
and the PM Selective of the nanofiltration membrane is created, the MWCO is 900, the maximum pressure is 60 bar, the maximum temperature is 50 ℃, and the optimum pH is 7.
The pressures referred to in the following examples are absolute pressures.
Optical purity:
an optical purity ee% (R-citronellal peak area in gas chromatography-S-citronellal peak area in gas chromatography)/(R-citronellal peak area in gas chromatography + S-citronellal peak area in gas chromatography);
conversion rate:
conversion rate ═ 100% - (neral peak area in gas chromatography + geranial peak area in gas chromatography)/total peak area in gas chromatography (desolvation);
cumulative number of conversions: the cumulative moles of catalytic substrate reacted per mole of catalyst.
Example 1
Separately, 2.094mg of RhCl were added under a nitrogen atmosphere3(0.01mmol) and 4.985mg of the above ligand (VI) (0.01mmol) were dissolved in 152g of a mixture of neral and geranial (neral: geranial 99:1, molar ratio of catalyst/substrate 0.001% calculated by the molar amount of rhodium atoms in the catalyst), added to a reaction kettle, the reaction pressure was adjusted to 100 bar (reaction pressure, absolute pressure) by injecting hydrogen, stirring was started and the reaction system was heated to 50 ℃, the pressure of hydrogen in the reaction kettle was kept constant during the reaction, and after 8h of reaction, gas phase detection was taken and the conversion rate was 99.5% and the optical purity of the product R-citronellal was 92.3%.
Taking out the reaction system materials, cooling to 30 ℃, then obtaining a feed liquid with the viscosity of 5cp (25 ℃), the pH value of 7.5, performing primary filtration by using a STARMEM228 nanofiltration membrane, wherein the catalyst concentration is 0.001 mol%, the filtration temperature is 25 ℃, the filtration pressure is 20 bar (absolute pressure), thus obtaining 7.8g of a catalyst concentrated solution, adding the same raw materials (152g of a mixture of neral and geranial, the neral: geranial is 99:1) into the catalyst concentrated solution after the primary filtration, uniformly mixing, obtaining the feed liquid with the viscosity of 5cp (25 ℃), the pH value of 7.3, performing secondary filtration by using a DM900 nanofiltration membrane, wherein the catalyst concentration is 0.001 and 05 mol%, the filtration temperature is 20 ℃, and the filtration pressure is 30 bar (absolute pressure), thus obtaining 154.2g of a filtrate, namely the separated and purified raw materials and a catalyst mixture. Adding the mixture into a reaction kettle, regulating the reaction pressure to 100 bar (reaction pressure, absolute pressure) by injecting hydrogen, starting stirring, heating the reaction system to 50 ℃, keeping the pressure of the hydrogen in the reaction kettle unchanged in the reaction process, and sampling gas phase detection after reacting for 8 hours to obtain the product R-citronellal with the conversion rate of 99.5 percent and the optical purity of 92.5 percent.
The above-mentioned process of applying the catalyst is repeated 18 times, and the conversion rates obtained by gas phase detection are 99.3%, 99.5%, 99.2%, 99.1%, 99.2%, 99.4%, 99.5%, 99.3%, 99.4%, 99.1%, 99.0%, 99.6%, 99.4%, 99.3%, 99.1%, 99.2%, and 99.4%, respectively, and the optical purities are 92.2%, 92.4%, 92.1%, 92.5%, 92.3%, 92.1%, 92.5%, 92.7%, 92.5%, 92.3%, 92.1%, 92.4%, 92.6%, 92.7%, 92.3%, 92.2%, and 92.2%, respectively. The total cumulative conversion based on R-citronellal yield was 1,744,828.
Example 2
Under a nitrogen gas atmosphere, 20.29mg of Rh (cod) was added2BF4(0.05mmol) and 44.02mg of the above ligand (VII) (0.1mmol) were dissolved in 152g of a mixture of neral and geranial (neral: geranial: 1:99, molar ratio of catalyst/substrate is 0.005% calculated by the mole of rhodium atom in the catalyst), added to a reaction kettle, the reaction pressure was adjusted to 50 bar (reaction pressure, absolute pressure) by injecting hydrogen, stirring was started and the reaction system was heated to 25 ℃, the pressure of hydrogen in the reaction kettle was kept constant during the reaction, after 6h of reaction, gas phase detection was taken out, and the conversion rate was 99.3% and the optical purity of the product R-citronellal was 92.6%.
Taking out the reaction system materials, cooling to 20 ℃, then obtaining a filtrate with the viscosity of 6cp (25 ℃), the pH value of 8.2, performing primary filtration by using an MPF-60 nanofiltration membrane, wherein the concentration of the catalyst is 0.005 mol%, the filtration temperature is 10 ℃, the filtration pressure is 5 bar (absolute pressure), thus obtaining 7.4g of a catalyst concentrated solution, adding the same raw materials (152g of a mixture of neral and geranial, the neral is geranial: 1:99) into the catalyst concentrated solution after the primary filtration, uniformly mixing, obtaining the viscosity of the feed solution with the viscosity of 5cp (25 ℃), the pH value of 7.8, performing secondary filtration by using a DM900 nanofiltration membrane, wherein the concentration of the catalyst is 0.00524 mol%, the filtration temperature is 10 ℃, and the filtration pressure is 20 bar (absolute pressure), thus obtaining 154.6g of the filtrate, namely the separated and purified raw materials and the catalyst mixture. Adding the mixture into a reaction kettle, regulating the reaction pressure to 50 bar (reaction pressure, absolute pressure) by injecting hydrogen, starting stirring, heating the reaction system to 25 ℃, keeping the pressure of the hydrogen in the reaction kettle unchanged in the reaction process, and sampling gas phase detection after 6 hours of reaction to obtain the product R-citronellal with the conversion rate of 99.1 percent and the optical purity of 92.5 percent.
The above-mentioned process of catalyst application is repeated 18 times, and the conversion rates obtained by gas phase detection are 99.3%, 99.5%, 99.2%, 99.6%, 99.3%, 99.2%, 99.4%, 99.5%, 99.3%, 99.4%, 99.3%, 99.2%, 99.1%, 99.5%, 99.3%, 99.6%, 99.4%, and corresponding optical purities are 92.3%, 92.6%, 92.8%, 92.6%, 92.9%, 92.3%, 92.5%, 92.6%, 92.3%, 92.2%, 92.1%, 92.6%, 92.4%, 92.6%, 92.3%, 92.5%, 92.2%, respectively. The total cumulative conversion based on R-citronellal yield was 350,376.
Example 3
2.132mg of Rh were added under a nitrogen atmosphere6(CO)16(0.002mmol) and 0.1976mg of the above ligand (VIII) (0.0004mmol) were dissolved in 304g of a mixture of neral and geranial (neral: geranial 99:1, molar ratio of catalyst/substrate 0.0001% calculated by the molar amount of rhodium atoms in the catalyst), added to a reaction kettle, the reaction pressure was adjusted to 80 bar (reaction pressure, absolute pressure) by injecting hydrogen, stirring was started and the reaction system was heated to 90 ℃, the pressure of hydrogen in the reaction kettle was kept constant during the reaction, and after 9 hours of reaction, gas phase detection was taken out to obtain a conversion of 98.5% and an optical purity of the product R-citronellal of 91.6%.
Taking out the reaction system materials, cooling to 40 ℃, then obtaining a feed liquid with the viscosity of 6cp (25 ℃), the pH value of 7.3, performing primary filtration by using a STARMEM228 nanofiltration membrane, wherein the concentration of the catalyst is 0.0001 mol%, the filtration temperature is 35 ℃, the filtration pressure is 50 bar (absolute pressure), thus obtaining 16.4g of a catalyst concentrated solution, adding the same raw materials (304g of a mixture of neral and geranial, the neral: geranial is 99:1) into the catalyst concentrated solution after the primary filtration, uniformly mixing, obtaining the viscosity of the feed liquid of 5cp (25 ℃), the pH value of 7.1, performing secondary filtration by using a PM Selective nanofiltration membrane, wherein the concentration of the catalyst is 0.000105 mol%, the filtration temperature is 30 ℃, and the filtration pressure is 40 bar (absolute pressure), thus obtaining 307.6g of a filtrate, and obtaining a mixture of the separated and purified raw materials and the catalyst. Adding the product into a reaction kettle, adjusting the reaction pressure to 80 bar (reaction pressure, absolute pressure) by injecting hydrogen, starting stirring, heating the reaction system to 90 ℃, keeping the pressure of the hydrogen in the reaction kettle unchanged in the reaction process, and after reacting for 9 hours, sampling and detecting by gas phase to obtain the product with the conversion rate of 98.8 percent and the optical purity of the product R-citronellal of 91.4 percent.
The above-mentioned process of applying the catalyst was repeated 18 times, and the conversion rates obtained by gas phase detection were 98.6%, 98.8%, 98.5%, 98.8%, 98.7%, 98.5%, 98.6%, 98.4%, 98.7%, 98.4%, 98.2%, 98.4%, 98.6%, 98.4%, 98.5%, 98.3%, and the corresponding optical purities were 91.4%, 91.6%, 91.7%, 91.3%, 91.5%, 91.3%, 91.4%, 91.6%, 91.8%, 91.6%, 91.7%, 91.4%, 91.6%, 91.5%, 91.7%, 91.8%, 91.5%, and 91.4%, respectively. The total cumulative conversion based on R-citronellal yield was 14,948,240.
Example 4
Under a nitrogen gas atmosphere, 13.44mg of [ Rh (cod) OH]2(0.02mmol) and 5.511mg of the above ligand (IX) (0.01mmol) were dissolved in 152g of a mixture of neral and geranial (neral: geranial: 1:99, molar ratio of catalyst/substrate is 0.002% calculated by the molar amount of rhodium atoms in the catalyst), added to a reaction kettle, the reaction pressure was adjusted to 40 bar (reaction pressure, absolute pressure) by injecting hydrogen, stirring was started and the reaction system was heated to 65 ℃, the pressure of hydrogen in the reaction kettle was kept constant during the reaction, after 10h of reaction, a sample was taken and gas phase detection was performed, and the conversion rate was 99.5% and the optical purity of the product R-citronellal was 93.7%.
Taking out the reaction system materials, cooling to 40 ℃, then obtaining a feed liquid with the viscosity of 5cp (25 ℃), the pH value of 8.3, performing primary filtration by using an MPF-60 nanofiltration membrane, wherein the concentration of the catalyst is 0.002 mol%, the filtration temperature is 35 ℃, and the filtration pressure is 50 bar (absolute pressure), thus obtaining 7.9g of a catalyst concentrated solution, adding the same raw materials (152g of a mixture of neral and geranial, the neral: geranial is 1:99) into the catalyst concentrated solution after the primary filtration, uniformly mixing, obtaining the feed liquid with the viscosity of 6cp (25 ℃), the pH value of 6.8, performing secondary filtration by using a PM Selective nanofiltration membrane, wherein the concentration of the catalyst is 0.00211 mol%, the filtration temperature is 30 ℃, and the filtration pressure is 40 bar (absolute pressure), thus obtaining 154.1g of a filtrate, namely a mixture of the separated and purified raw materials and the catalyst. Adding the product into a reaction kettle, regulating the reaction pressure to 40 bar (reaction pressure, absolute pressure) by injecting hydrogen, starting stirring, heating the reaction system to 65 ℃, keeping the pressure of the hydrogen in the reaction kettle unchanged in the reaction process, and sampling gas phase detection after 10 hours of reaction to obtain the product with the conversion rate of 99.4 percent and the optical purity of the product R-citronellal of 93.4 percent.
The above-mentioned process of applying the catalyst was repeated 18 times, and the conversion rates obtained by gas phase detection were 99.2%, 99.4%, 99.6%, 99.7%, 99.4%, 99.5%, 99.3%, 99.6%, 99.4%, 99.5%, 99.4%, 99.3%, 99.6%, 99.4%, 99.2%, 99.3%, 99.7%, and corresponding optical purities were 93.4%, 93.6%, 93.3%, 93.2%, 93.4%, 93.6%, 93.5%, 93.8%, 93.6%, 93.3%, 93.7%, 93.3%, 93.5%, 93.7%, 93.4%, 93.5%, 93.3%, and 93.6%, respectively. The total cumulative conversion based on R-citronellal yield was 893,744.
Example 5
Under a nitrogen atmosphere, 28.03mg of Rh (OAc) was added3(0.1mmol) and 4.804mg of the above ligand (X) (0.01mmol) were dissolved in 152g of a mixture of neral and geranial (neral: geranial: 1:99, molar ratio of catalyst/substrate is 0.01% calculated by the molar amount of rhodium atoms in the catalyst), added to a reaction kettle, the reaction pressure was adjusted to 10 bar (reaction pressure, absolute pressure) by injecting hydrogen, stirring was started and the reaction system was heated to 120 ℃, the pressure of hydrogen in the reaction kettle was kept constant during the reaction, and after 24 hours of reaction, gas phase detection was taken out to obtain a conversion of 98.3% and an optical purity of the product R-citronellal of 91.5%.
Taking out the reaction system materials, cooling to 35 ℃, obtaining a feed liquid with the viscosity of 6cp (25 ℃) and the pH value of 7.1, performing primary filtration by using a STARMEM228 nanofiltration membrane, wherein the catalyst concentration is 0.01 mol%, the filtration temperature is 25 ℃, the filtration pressure is 30 bar (absolute pressure), obtaining 7.3g of a catalyst concentrated solution, adding the same raw materials (152g of a mixture of neral and geranial, the neral: geranial is 1:99) into the catalyst concentrated solution after the primary filtration, uniformly mixing, obtaining the feed liquid with the viscosity of 5cp (25 ℃) and the pH value of 6.5, performing secondary filtration by using a DM900 nanofiltration membrane, wherein the catalyst concentration is 0.0105 mol%, the filtration temperature is 25 ℃, and the filtration pressure is 40 bar (absolute pressure), obtaining 154.9g of a filtrate, and obtaining a mixture of the separated and purified raw materials and the catalyst. Adding the mixture into a reaction kettle, regulating the reaction pressure to 10 bar (reaction pressure, absolute pressure) by injecting hydrogen, starting stirring, heating the reaction system to 120 ℃, keeping the pressure of the hydrogen in the reaction kettle unchanged in the reaction process, and sampling gas phase detection after 24 hours of reaction to obtain the product R-citronellal with the conversion rate of 98.4 percent and the optical purity of 91.5 percent.
The above catalyst application process was repeated 38 times, and the conversion rates obtained by gas phase detection were 98.5%, 98.3%, 98.6%, 98.3%, 98.4%, 98.2%, 98.6%, 98.7%, 98.6%, 98.5%, 98.3%, 98.2%, 98.3%, 98.6%, 98.4%, 98.3%, 98.2%, 98.6%, 98.3%, 98.2%, 98.4%, 98.6%, 98.8%, 98.7%, 98.8%, 98.5%, 98.7%, 98.5%, 98.3%, 98.6%, 98.9%, 98.2%, 98.4%, 98.6%, 98.1%, and 97.6% in this order. Corresponding to optical purities of 91.7%, 91.6%, 91.4%, 91.5%, 91.6%, 91.3%, 91.6%, 91.4%, 91.2%, 91.3%, 91.2%, 91.4%, 91.7%, 91.4%, 91.8%, 91.5%, 91.9%, 91.7%, 91.5%, 91.8%, 91.6%, 91.5%, 91.4%, 91.2%, 91.7%, 91.3%, 91.6%, 91.4%, 91.5%, 91.8%, 91.2%, 91.3%, 91.4%, 91.5%, 91.3%, and 91.7% in that order. The total cumulative conversion based on R-citronellal yield was 213,027.
Example 6
Respectively reacting under nitrogen atmosphere25.94mg Rh(CO)2acac (0.1mmol) and 12.13mg of the above ligand (XI) (0.025mmol) were dissolved in 304g of a mixture of neral and geranial (neral: geranial: 1:99, molar ratio of catalyst/substrate: 0.005% calculated by the mole of rhodium atom in the catalyst), added to a reaction vessel, the reaction pressure was adjusted to 55 bar (reaction pressure, absolute pressure) by injecting hydrogen gas, stirring was started and the reaction system was maintained at 0 ℃, the pressure of hydrogen gas in the reaction vessel was kept constant during the reaction, and after 12 hours of reaction, gas phase detection was taken and the conversion rate was 98.3% and the optical purity of the product R-citronellal was 91.5%.
Taking out the reaction system materials, heating to 43 ℃, then obtaining a feed liquid with the viscosity of 4cp (25 ℃) and the pH value of 7.1, performing primary filtration by using a STARMEM228 nanofiltration membrane, wherein the catalyst concentration is 0.005 mol%, the filtration temperature is 40 ℃, the filtration pressure is 35 bar (absolute pressure), thus obtaining 16.2g of a catalyst concentrated solution, adding the same raw materials (304g of a mixture of neral and geranial, the neral: geranial is 1:99) into the catalyst concentrated solution after the primary filtration, uniformly mixing, obtaining the feed liquid with the viscosity of 4cp (25 ℃) and the pH value of 6.6, performing secondary filtration by using a DM900 nanofiltration membrane, wherein the catalyst concentration is 0.00527 mol%, the filtration temperature is 40 ℃, and the filtration pressure is 35 bar (absolute pressure), thus obtaining 307.8g of a filtrate, namely a mixture of the separated and purified raw materials and the catalyst. Adding the product into a reaction kettle, regulating the reaction pressure to 55 bar (reaction pressure, absolute pressure) by injecting hydrogen, starting stirring, keeping the reaction system at 0 ℃, keeping the pressure of the hydrogen in the reaction kettle unchanged in the reaction process, and after reacting for 12 hours, sampling and detecting a gas phase to obtain the product with the conversion rate of 98.5 percent and the optical purity of the product R-citronellal of 91.5 percent.
The above-mentioned process of applying the catalyst was repeated 18 times, and the conversion rates obtained by gas phase detection were 98.4%, 98.2%, 98.5%, 98.3%, 98.6%, 98.4%, 98.3%, 98.6%, 98.5%, 98.4%, 98.2%, 98.1%, 98.2%, 98.5%, 98.6%, 98.4%, 98.7%, 98.5%, and corresponding optical purities were 91.4%, 91.3%, 91.2%, 91.5%, 91.3%, 91.6%, 91.7%, 91.8%, 91.6%, 91.5%, 91.4%, 91.7%, 91.5%, 91.4%, 91.3%, 91.7%, 91.8%, and 91.6%, respectively. The total cumulative conversion based on R-citronellal yield was 290,291.
Comparative example 1
This comparative example is prior art, using CN 101039894B.
Under a nitrogen atmosphere, 28.03mg of Rh (OAc) was added3(0.1mmol) and 4.804mg of the above ligand (X) (0.01mmol) were dissolved in 152g of a mixture of neral and geranial (neral: geranial: 1:99, molar ratio of catalyst/substrate is 0.01% calculated by the molar amount of rhodium atoms in the catalyst), added to a reaction kettle, the reaction pressure was adjusted to 10 bar (reaction pressure, absolute pressure) by injecting hydrogen, stirring was started and the reaction system was heated to 120 ℃, the pressure of hydrogen in the reaction kettle was kept constant during the reaction, and after 24 hours of reaction, gas phase detection was taken out to obtain a conversion of 98.3% and an optical purity of the product R-citronellal of 91.5%. Distilling under reduced pressure at the pressure of 400PaA and the temperature of 80 ℃ to evaporate 144.7g of product R-citronellal, then adding 152g of mixture of neral and geranial (neral: geranial is 1:99), adjusting the reaction pressure to 10 bar (reaction pressure, absolute pressure) by injecting hydrogen, starting stirring and heating the reaction system to 120 ℃, keeping the pressure of the hydrogen in the reaction kettle unchanged in the reaction process, and after reacting for 24h, sampling gas phase detection to obtain the product R-citronellal with the conversion rate of 36.4% and the optical purity of 52.6%. The number of revolutions per minute based on the R-citronellal yield was 7,156.
Comparative example 2
In contrast to example 1, except that no DM900 nanofiltration membrane was used for the secondary filtration.
Separately, 2.094mg of RhCl were added under a nitrogen atmosphere3(0.01mmol) and 4.985mg of the above ligand (VI) (0.01mmol) were dissolved in 152g of a mixture of neral and geranial (neral: geranial 99:1, molar ratio of catalyst/substrate 0.001% calculated by the molar amount of rhodium atom in the catalyst), added to a reaction kettle, the reaction pressure was adjusted to 100 bar (reaction pressure, absolute pressure) by injecting hydrogen, stirring was started and the reaction system was heated to 50 ℃, the pressure of hydrogen in the reaction kettle was kept constant during the reaction, and after 8h of reaction, gas phase detection was taken and the conversion rate was 99.3% and optical purity was 92.5%.
Taking out the reaction system materials, cooling to 30 ℃, then obtaining a material liquid with the viscosity of 5cp (25 ℃) and the pH value of 7.5, performing primary filtration by using a STARMEM228 nanofiltration membrane, filtering at 25 ℃, filtering at 20 bar (absolute pressure) to obtain 7.8g of a catalyst concentrated solution, adding the same raw materials (152g of a mixture of neral and geranial, neral: geranial being 99:1) into the catalyst concentrated solution after the primary filtration, uniformly mixing, adding the catalyst concentrated solution into a reaction kettle, adjusting the reaction pressure to 100 bar (reaction pressure, absolute pressure) by injecting hydrogen, stirring and heating the reaction system to 50 ℃, keeping the pressure of the hydrogen in the reaction kettle unchanged during the reaction, and after 8 hours of reaction, sampling gas phase detection to obtain a product R-citronellal conversion rate of 56.6% and the optical purity of 92.7%. The number of revolutions per minute based on the R-citronellal yield was 112,408.
The results of the above examples and comparative examples show that the activity and stability of the mechanically applied catalyst are significantly improved by the two-stage nanofiltration membrane filtration, and a higher cumulative conversion number is realized.
Claims (16)
1. A process for the preparation of R-citronellal, comprising the steps of:
s1: carrying out asymmetric hydrogenation reaction on reaction substrates neral and/or geranial in the presence of a catalyst to generate R-citronellal;
s2: performing primary nanofiltration separation on the S1 reaction liquid by using a nanofiltration membrane M to obtain a catalyst concentrated solution and a dialysate containing a product R-citronellal, and separating the dialysate to obtain a reaction product citronellal without a catalyst;
s3: adding the next batch of reaction raw materials into the concentrated catalyst solution of S2, performing secondary nanofiltration separation by using a nanofiltration membrane N to obtain dialysate containing a mixture of the purified reaction raw materials and the catalyst, directly performing the next batch of reaction on the mixture, and separating the dialysate to recover the catalyst;
wherein the catalyst in S1 is a transition metal catalyst, the transition metal is a metal element of group VIII in the periodic table of elements, and the catalyst is obtained by reacting a transition metal compound which can be dissolved in a reaction system with an optically active ligand containing two phosphorus atoms;
wherein the nanofiltration membrane M used in the first-stage nanofiltration separation in S2 is a TFC type nanofiltration membrane;
and the nanofiltration membrane N used for the secondary nanofiltration separation in the S3 is an ISA type nanofiltration membrane.
2. The method according to claim 1, wherein the molar ratio of the transition metal atom in the transition metal compound to the optically active ligand comprising two phosphorus atoms in S1 is (0.5-10): 1.
3. the method according to claim 1, wherein the molar ratio of the transition metal atom in the transition metal compound to the optically active ligand comprising two phosphorus atoms in S1 is (0.5-1): 1.
4. the method according to claim 1, wherein the transition metal compound in S1 is one or more of a transition metal halide, a transition metal carbonate and a transition metal complex.
5. The method according to claim 4, wherein the transition metal element in the transition metal compound in S1 is rhodium;
the transition metal complex is selected from a complex formed by coordination of transition metal and one or more of carbonyl compounds, acetylacetone compounds, hydroxyl compounds, cyclooctadiene, norbornadiene, cyclooctene, methoxy compounds, acetyl compounds, aliphatic carboxylic acid compounds or aromatic carboxylic acid compounds.
6. The method according to claim 4, wherein the transition metal compound in S1 is selected from one or more of transition metal halides, complexes of transition metals coordinated with carbonyl compounds, complexes of transition metals coordinated with cyclooctadiene, and complexes of transition metals coordinated with acetyl compounds.
7. The method according to claim 4, wherein the transition metal compound of S1 is selected from RhCl3、Rh(OAc)3、Rh(cod)2BF4、[Rh(cod)Cl]2、Rh(CO)2acac、[Rh(cod)OH]2、[Rh(cod)OMe]2、Rh4(CO)12And Rh6(CO)16Wherein "acac" is an acetylacetone ligand and "cod" is a cyclooctadiene ligand.
8. The method according to claim 1, wherein the optically active ligand comprising two phosphorus atoms in S1 is selected from one or more of the following ligands of formula (iv) and formula (v):
wherein R is1、R2Each independently of the others, an unbranched alkyl radical having from 1 to 20 carbon atoms, a branched alkyl radical OR a cyclic alkyl radical, optionally bearing one OR more olefinic double bonds, and/OR, optionally, one OR more identical OR different radicals from the group OR9、NR10R11Halogen, C6-C10Aryl and C3-C9A substituent of heteroaryl; or R1And R2Taken together to form a ring having from 4 to 20 ring-forming carbon atoms, and
R3、R4each independently hydrogen or straight chain C1-C4Alkyl or branched C1-C4Alkyl, and
R5、R6、R7、R8each independently is C6-C10Aryl, and each may optionally bear one or more substituents selected from C1-C4Alkyl radical, C6-C10Aryl radical, C1-C4Substituents of alkoxy and amino, and
R9、R10、R11each independently is hydrogen, C1-C4Alkyl radical, C6-C10Aryl radical, C7-C12Aralkyl or C7-C12Alkylaryl, or R10、R11Taken together to form an alkylene chain having 2 to 5 carbon atoms and optionally interrupted by an N atom or an O atom.
9. The process according to claim 1, characterized in that the asymmetric hydrogenation in S1 is carried out at a pressure of 10-100 bar absolute; the reaction temperature is 0-120 ℃.
10. The process according to claim 1, characterized in that the asymmetric hydrogenation in S1 is carried out at a pressure of 50-80 bar absolute; the reaction temperature is 25-90 ℃.
11. The method as claimed in claim 1, wherein the nanofiltration membrane M used in the first nanofiltration separation in S2 is a STARMEM series product from GRACE or MPF-60 from KOCH.
12. The method as claimed in claim 1, wherein the nanofiltration membrane M used in the first-stage nanofiltration separation in S2 is rice STARMEM 228.
13. The method as claimed in claim 1, wherein the concentration of the first stage nanofiltration separation filtration catalyst in S2 is 0.000,1mol% to 0.1mol%, based on the total molar amount of the substrate;
and/or the temperature of the feed liquid is 10-40 ℃, the pH range of the feed liquid is 7.1-8.3, the filtration pressure is 5-50 bar absolute pressure, and the viscosity of the solution at 25 ℃ is less than 10 cp.
14. The method as claimed in claim 1, wherein the nanofiltration membrane N used in the secondary nanofiltration separation in S3 is derived from company DM series products or company PM selected.
15. The method of claim 1, wherein nanofiltration membrane N used in the secondary nanofiltration separation in S3 is the company DM 900.
16. The method according to claim 1, wherein the concentration of the secondary nanofiltration separation filtration catalyst in S3 is 0.000,1mol% to 0.1mol%, based on the total molar amount of the substrates;
and/or the temperature of the feed liquid is 10-40 ℃, the pH range of the feed liquid is 6.5-7.8, the filtration pressure is 20-40 bar absolute pressure, and the viscosity of the solution at 25 ℃ is less than 10 cp.
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| CN110872217A (en) * | 2019-12-09 | 2020-03-10 | 万华化学集团股份有限公司 | Preparation method of citronellal with optical activity |
| CN111056932A (en) * | 2019-12-09 | 2020-04-24 | 万华化学集团股份有限公司 | Method for preparing optical activity citronellal |
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| CN110872217A (en) * | 2019-12-09 | 2020-03-10 | 万华化学集团股份有限公司 | Preparation method of citronellal with optical activity |
| CN111056932A (en) * | 2019-12-09 | 2020-04-24 | 万华化学集团股份有限公司 | Method for preparing optical activity citronellal |
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