CN115557993A - Self-supported chiral phosphoric acid catalyst and synthesis method thereof - Google Patents
Self-supported chiral phosphoric acid catalyst and synthesis method thereof Download PDFInfo
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 52
- 238000001308 synthesis method Methods 0.000 title abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 7
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 31
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 13
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 claims description 10
- 229920000075 poly(4-vinylpyridine) Polymers 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 5
- 238000000944 Soxhlet extraction Methods 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- 229960001701 chloroform Drugs 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 7
- 238000005859 coupling reaction Methods 0.000 abstract description 8
- 230000008878 coupling Effects 0.000 abstract description 4
- 238000010168 coupling process Methods 0.000 abstract description 4
- 239000000543 intermediate Substances 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000012043 crude product Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 229940125904 compound 1 Drugs 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000005347 biaryls Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- -1 hydroxyl hydrogen Chemical compound 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010512 small scale reaction Methods 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
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- B01J31/0257—Phosphorus acids or phosphorus acid esters
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Abstract
The invention relates to a self-supported chiral phosphoric acid catalyst and a synthesis method thereof, which are characterized in that the self-supported chiral phosphoric acid catalyst is a polymer shown in a formula I, and the structural formula of the polymer shown in the formula I is as follows:
wherein n is more than or equal to 2; ar is
i-Pr is an isopropyl group, and Ph is an aromatic hydrocarbon group.Firstly, taking a chiral phosphoric acid catalyst TRIP as a framework, and then carrying out Scholl coupling reaction under mild coupling conditions to prepare the self-supported chiral phosphoric acid catalyst, wherein the yield of the self-supported chiral phosphoric acid catalyst is up to 99%.
Description
Technical Field
The invention relates to the field of organic molecular catalysts, in particular to a self-supported chiral phosphoric acid catalyst and a synthesis method thereof.
Background
Asymmetric catalysis is a research hotspot in the field of organic synthetic chemistry at present, and can be divided into metal complex catalysts, organic molecular catalysts and biological enzyme catalysts according to the types of the catalysts. Among them, the organic molecular catalyst does not contain metal, is little affected by impurities in catalytic reaction, can realize specific catalytic reaction, is simple in experimental operation, mild in reaction condition and friendly to environment and organism, and has become a popular research field.
In the field of organic molecular catalysts, chiral phosphoric acid catalysts are protonic acid catalysts, and show excellent catalytic activity and stereoselectivity in addition reaction of nucleophilic reagents to imine and catalysis of chiral ions. Since Akiyama and Terada topic groups independently report chiral phosphoric acid catalysts respectively in 2004, chiral phosphoric acid derived from axial chiral biaryl represents a potential and widely applicable enantioselective organic catalyst through the development of nearly 20 years, and can be used for catalyzing various organic reactions. For example, as shown in FIG. 1, chiral phosphoric acid catalysts with BINOL, H8-BINOL and SPINOL as the skeleton have become the focus of the research field of chiral organic catalysis.
However, in view of the industrial application in this field, chiral phosphoric acid catalysts have problems, for example, chiral catalysts are difficult to synthesize and are very expensive; have high molecular weights, require the use of substantial amounts of catalyst to perform small-scale reactions even at low catalyst loadings; in addition, since homogeneous catalysts are easily soluble in organic solvents and are difficult to recover, these disadvantages limit the industrial application of chiral phosphoric acid catalysts in related reactions.
In recent years, a supported catalyst has attracted much attention because it has advantages of a simple reaction of a catalyst system, easy recovery of the catalyst, and recyclability. The heterogeneous catalyst not only reduces the total cost of the reaction, but also has advantages in the problems of separation and purification, metal residue and the like, and is more in line with the concept of green chemistry and sustainable development. However, the traditional supported catalyst has many negative factors, such as the activity and selectivity of the catalyst are reduced compared with those of a homogeneous catalyst, so that the preparation of a simple and efficient self-supported chiral phosphoric acid catalyst is needed.
Disclosure of Invention
Aiming at the prior art, the invention develops a self-supported chiral phosphoric acid catalyst, and the self-supported chiral phosphoric acid catalyst is prepared by taking a chiral phosphoric acid catalyst TRIP as a framework and then carrying out Scholl coupling reaction under mild coupling conditions, wherein the yield is up to 99%.
Based on the above, the invention provides a self-supported chiral phosphoric acid catalyst, which is a polymer shown in formula I, wherein the structural formula of the polymer shown in formula I is as follows:
wherein n is more than or equal to 2; ar is
i-Pr is isopropyl group, and Ph is an aromatic hydrocarbon group.
Further, the self-supported catalyst at least comprises the following raw materials: formula IICompound, POCl 3 、AlCl 3 An organic solvent;
wherein the structural formula of the compound shown in the formula II is as follows:
further, the organic solvent is any one of dichloromethane and trichloromethane.
The invention also aims to provide a synthesis method of the self-supported chiral phosphoric acid catalyst, which at least comprises the following steps:
and (3) carrying out a phosphoryl chloride reaction: taking a compound of a formula II and POCl 3 Reacting an organic solvent for 30-50h at 25-35 ℃ in an inert gas atmosphere to obtain an intermediate;
polymerization reaction: taking the intermediate and AlCl 3 And reacting the organic solvent for 45 to 50 hours at the temperature of between 56 and 60 ℃ in the atmosphere of inert gas, and purifying after the reaction is finished to obtain the polymer shown in the formula I.
Further, the intermediate has a structural formula:
further, the compound of formula II is reacted with POCl 3 The mass ratio of (1) to (2.5-3).
Further, the intermediate is reacted with AlCl 3 The mass ratio of (A) to (B) is 1.
Further, the purification step is that the obtained product is washed once by ethanol, twice by HCl solution and three times by ethanol respectively, then the product is subjected to soxhlet extraction by ethanol for 24 hours, and finally the product is dried in a vacuum oven at 70-80 ℃ for 20-28 hours.
Further, the compound of formula ii needs to be dried before the phosphorus oxychloride reaction.
Further, the drying step is to add the compound of formula II and a large excess of poly (4-vinylpyridine) to a dried Schlenk tube and dry under vacuum for 1-2h.
In conclusion, the invention has the following beneficial effects: the invention discloses a self-supported chiral phosphoric acid catalyst, which is prepared by taking a chiral phosphoric acid catalyst TRIP as a framework and then carrying out Scholl coupling reaction under mild coupling conditions, wherein the yield of the self-supported chiral phosphoric acid catalyst is up to 99%. The phosphoryl chloride reaction and the polymerization reaction can respectively react at the temperature of 25-35 ℃ and the temperature of 56-60 ℃, and the reaction conditions are relatively mild, thereby greatly reducing the total cost of the reaction.
Drawings
In order to more clearly illustrate the embodiments or technical solutions of the present invention, the drawings used in the embodiments or technical solutions of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 shows chiral phosphoric acid catalysts of BINOL, H8-BINOL and SPINOL skeleton in the background art.
FIG. 2 is a reaction scheme of the self-supported chiral phosphoric acid catalyst in the first example.
FIG. 3 shows a PXRD spectrum of a self-supported chiral phosphoric acid catalyst prepared according to an embodiment of the present invention.
FIG. 4 is an infrared spectrum of a self-supported chiral phosphoric acid catalyst prepared according to the first embodiment of the present invention.
FIG. 5 is a thermogravimetric plot of the self-supported chiral phosphoric acid catalyst prepared according to the first embodiment of the present invention.
FIG. 6 is an SEM image of a self-supported chiral phosphoric acid catalyst prepared according to a first embodiment of the present invention.
FIG. 7 is a TEM image of the self-supported chiral phosphoric acid catalyst prepared according to the first embodiment of the present invention.
FIG. 8 is an EDS mapping chart of the self-supported chiral phosphoric acid catalyst prepared in the first embodiment of the present invention.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
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 experimental procedures in the following examples are all conventional ones unless otherwise specified. Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified. In the quantitative tests in the following examples, three replicates were set, and the data are the mean value or the mean value ± standard deviation of the three replicates.
In addition, "and/or" in the whole text includes three schemes, taking a and/or B as an example, and includes a technical scheme a, a technical scheme B, and a technical scheme that a and B meet simultaneously; in addition, the technical solutions in the embodiments may be combined with each other, but it must be based on the realization of those skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The invention provides a self-supported chiral phosphoric acid catalyst which is a polymer shown in a formula I, wherein the structural formula of the polymer shown in the formula I is as follows:
wherein n is more than or equal to 2; ar is
i-Pr is isopropyl group, and Ph is an aromatic hydrocarbon group.
In some embodiments, the self-supported catalyst comprises at least the following feedstocks: shown in formula IICompound and POCl 3 、AlCl 3 An organic solvent;
wherein the structural formula of the compound shown in the formula II is as follows:
in some embodiments, the organic solvent is dichloromethane (CH) 2 Cl 2 ) Trichloromethane (CHCl) 3 ) Any one of them.
The invention also aims to provide a synthesis method of the self-supported chiral phosphoric acid catalyst, which at least comprises the following steps:
and (3) phosphorus oxychloride reaction: taking a compound of a formula II, POCl 3 Reacting an organic solvent for 30-50h at 25-35 ℃ in an inert gas atmosphere to obtain an intermediate;
polymerization reaction: taking the intermediate and AlCl 3 And reacting an organic solvent for 45-50h at 56-60 ℃ in an inert gas atmosphere, and purifying after the reaction is finished to obtain the polymer shown in the formula I.
Preferably, the reaction condition of the phosphorus oxychloride reaction is that the reaction is carried out for 40 hours at the temperature of 30 ℃.
Through the technical scheme, the reaction condition of the phosphorus oxychloride is mild.
Preferably, the reaction condition of the polymerization reaction is that the reaction is carried out for 48 hours at the temperature of 58 ℃.
By adopting the technical scheme, the polymerization reaction condition is mild, and the total cost of the reaction is greatly reduced.
In some embodiments, the intermediate has the formula:
in some embodiments, the compound of formula ii is reacted with POCl 3 The mass ratio of (A) to (B) is 1.
In some embodiments, the intermediate is reacted with AlCl 3 The mass ratio of (A) to (B) is 1.
Preferably, the intermediate is reacted with AlCl 3 Amount of substance (b)The ratio is 1.
In some embodiments, the purification step is to wash the resulting product with ethanol once, HCl solution twice, and ethanol three times, respectively, followed by soxhlet extraction with ethanol for 24h, and finally drying in a vacuum oven at 70-80 ℃ for 20-28h.
In some embodiments, the volume ratio of hydrochloric acid to water in the HCl solution is from 1.8 to 2.2.
Preferably, the volume ratio of hydrochloric acid to water is 2.
In some embodiments, the compound of formula ii is dried prior to the phosphorus oxychloride reaction.
In some embodiments, the drying step is performed by adding the compound of formula II and a large excess of poly (4-vinylpyridine) to a dry Schlenk tube and drying under vacuum for 1-2h.
In some embodiments, the poly (4-vinylpyridine) needs to be removed prior to polymerization.
In some embodiments, the mixture is filtered through cotton to remove poly (4-vinylpyridine)
Through the technical scheme, the poly (4-vinylpyridine) is alkali required in the reaction process of phosphorus oxychloride, and the stable intermediate phosphorus oxychloride can be obtained by using the poly (4-vinylpyridine). When the phosphoryl chloride reaction is finished, the poly (4-vinylpyridine) can be easily separated out before the polymerization reaction so as to prevent the subsequent polymerization reaction from being influenced.
In summary, the invention develops a self-supported chiral phosphoric acid catalyst, and the self-supported chiral phosphoric acid catalyst is prepared by taking a chiral phosphoric acid catalyst TRIP as a framework and then performing a Scholl coupling reaction under mild coupling conditions, wherein the yield of the self-supported chiral phosphoric acid catalyst is as high as 99%. The phosphorus oxychloride reaction and the polymerization reaction can be carried out under the conditions of 25-35 ℃ and 56-60 ℃ respectively, and the reaction conditions are relatively mild, so that the total cost of the reaction is greatly reduced.
Example one
In this example, the specific structure of the compound represented by formula ii is:
is denoted as compound-1.
Characterization of compound-1:
1 H NMR(400MHz,Chloroform-d)δ7.89(d,J＝8.0Hz,2H),7.79(s,2H),7.44-7.29(m,6H),7.20-7.12(m,4H),4.95(s,2H),2.99(h,J＝6.9Hz,2H),2.87(p,J＝6.8Hz,2H),2.72(hept,J＝6.9Hz,2H),1.33(s,12H),1.22(d,J＝6.9Hz,6H),1.12(dd,J＝9.3,6.9Hz,12H),1.06(d,J＝6.9Hz,6H)。
the specific synthesis process of the self-supported chiral phosphoric acid catalyst is as follows:
s1, 1mmol of compound-1 and 10mmol of poly (4-vinylpyridine) were taken up and added to a dry Schlenk tube, followed by drying under vacuum for 1h to give a mixture.
S2, under the nitrogen atmosphere, adding 5mLCH 2 Cl 2 And 3mmol of POCl 3 Adding to the mixture obtained in step S1, reacting at 30 ℃ for 40h, filtering the mixture through cotton to remove poly (4-vinylpyridine); the solvent was then evaporated to give a pale yellow intermediate; the intermediate was used as crude without further purification;
wherein the structural formula of the generated intermediate is as follows:
characterization of the above intermediates:
1 H NMR(400MHz,Chloroform-d)δ7.89(d,J＝8.0Hz,2H),7.79(s,2H),7.44-7.29(m,6H),7.20-7.12(m,4H),2.99(h,J＝6.9Hz,2H),2.87(p,J＝6.8Hz,2H),2.72(hept,J＝6.9Hz,2H),1.33(s,12H),1.22(d,J＝6.9Hz,6H),1.12(dd,J＝9.3,6.9Hz,12H),1.06(d,J＝6.9Hz,6H)。
when the hydrogen spectra of compound-1 and the intermediate are compared, the hydroxyl hydrogen on compound-1 is replaced after the phosphoryl chloride reaction is completed.
S3, taking 160mgAlCl in nitrogen atmosphere 3 77mg of intermediate formed in step S2, 1mLCHCl is added 3 In the solution, the solution is magnetically stirred for 48 hours at the temperature of 58 ℃, then is kept stand, and the crude product is taken out and precipitated.
And S4, washing the precipitate crude product obtained in the step S3 with ethanol once, washing the precipitate crude product with 6mol/L HCl solution twice and washing the precipitate crude product with ethanol three times in sequence, performing Soxhlet extraction on the precipitate crude product with ethanol for 24 hours, and drying the precipitate crude product in a vacuum oven at 75 ℃ for 24 hours to obtain a black solid which is a self-supported chiral phosphoric acid catalyst, wherein the yield of the catalyst is 99%.
Wherein the structural formula of the generated self-supported chiral phosphoric acid catalyst is as follows:
example a specific reaction scheme is shown in figure 2.
The self-supported chiral phosphoric acid catalyst synthesized in example one was characterized, and the results are shown in fig. 3 to 8.
As shown in FIGS. 3 to 8, the formation of the self-supported chiral phosphoric acid catalyst in the first example was confirmed.
The technical features of the embodiments described above can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, however, as long as there is no contradiction between the combinations of the technical features, the scope of the present description should be considered as being included in the description of the present specification.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A self-supported chiral phosphoric acid catalyst is characterized in that the catalyst is a polymer shown as a formula I,
the structural formula of the polymer shown in the formula I is as follows:
wherein n is more than or equal to 2; ar is
i-Pr is isopropyl group, and Ph is an aromatic hydrocarbon group.
2. The self-supported chiral phosphoric acid catalyst according to claim 1, wherein: at least comprises the following raw materials: a compound represented by the formula II, POCl 3 、AlCl 3 An organic solvent;
wherein the structural formula of the compound shown in the formula II is as follows:
3. the self-supported chiral phosphoric acid catalyst of claim 2, wherein: the organic solvent is any one of dichloromethane and trichloromethane.
4. A method for synthesizing a self-supported chiral phosphoric acid catalyst according to any one of claims 1 to 3, comprising at least the following steps:
and (3) phosphorus oxychloride reaction: taking a compound of a formula II and POCl 3 Reacting an organic solvent for 30-50h at 25-35 ℃ in an inert gas atmosphere to obtain an intermediate;
polymerization reaction: taking the intermediate and AlCl 3 And reacting the organic solvent for 45 to 50 hours at the temperature of between 56 and 60 ℃ in the atmosphere of inert gas, and purifying after the reaction is finished to obtain the polymer shown in the formula I.
5. The method for synthesizing the self-supported chiral phosphoric acid catalyst according to claim 4, wherein the method comprises the following steps: junction of said intermediateThe structure formula is:
6. the method for synthesizing the self-supported chiral phosphoric acid catalyst according to claim 4, wherein the method comprises the following steps: the compound of formula II and POCl 3 The mass ratio of (1) to (2.5-3).
7. The method for synthesizing the self-supported chiral phosphoric acid catalyst according to claim 4, wherein the method comprises the following steps: the intermediate reacts with AlCl 3 The mass ratio of (A) to (B) is 1.
8. The method for synthesizing the self-supported chiral phosphoric acid catalyst according to claim 4, wherein the method comprises the following steps: the purification step is that the obtained product is washed once by ethanol, twice by HCl solution and three times by ethanol respectively, then the product is subjected to Soxhlet extraction by ethanol for 24 hours, and finally the product is dried in a vacuum oven at 70-80 ℃ for 20-28 hours.
9. The method for synthesizing the self-supported chiral phosphoric acid catalyst according to claim 4, wherein the method comprises the following steps: the compound of formula II needs to be dried before the phosphorus oxychloride reaction.
10. The method for synthesizing the self-supported chiral phosphoric acid catalyst according to claim 9, wherein the method comprises the following steps: the drying step was carried out by adding the compound of formula II and a large excess of poly (4-vinylpyridine) to a dry Schlenk tube and drying under vacuum for 1-2h.
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| US20210324121A1 (en) * | 2018-08-17 | 2021-10-21 | The University Of North Carolina At Chapel Hill | Polyvinyl esters and methods related thereto |
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| US20010031887A1 (en) * | 2000-03-13 | 2001-10-18 | Junji Inanaga | Optically active phosphate derivative and its use |
| US20210324121A1 (en) * | 2018-08-17 | 2021-10-21 | The University Of North Carolina At Chapel Hill | Polyvinyl esters and methods related thereto |
| CN112778505A (en) * | 2021-01-26 | 2021-05-11 | 中国科学院青岛生物能源与过程研究所 | Synthesis method of gradual change type polyester |
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