CN112679394A - Preparation method of styrene monomer containing chiral sulfoxide - Google Patents
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- 150000003462 sulfoxides Chemical class 0.000 title claims abstract description 45
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 35
- 239000008103 glucose Substances 0.000 claims abstract description 35
- 239000012074 organic phase Substances 0.000 claims abstract description 33
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 18
- -1 (4-vinyl phenyl) magnesium chloride Grignard reagent Chemical class 0.000 claims abstract description 17
- LURSUHVHQZXABT-UHFFFAOYSA-N methanesulfinyl chloride Chemical compound CS(Cl)=O LURSUHVHQZXABT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000010791 quenching Methods 0.000 claims abstract description 13
- 230000000171 quenching effect Effects 0.000 claims abstract description 13
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 9
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- SCBOJHSGBNGFHZ-UHFFFAOYSA-N 1-ethenyl-4-methylsulfinylbenzene Chemical compound CS(=O)C1=CC=C(C=C)C=C1 SCBOJHSGBNGFHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000006467 substitution reaction Methods 0.000 claims abstract description 5
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 26
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 3
- KEJGAYKWRDILTF-JDDHQFAOSA-N (3ar,5s,6s,6ar)-5-[(4r)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-6-ol Chemical compound O1C(C)(C)OC[C@@H]1[C@@H]1[C@H](O)[C@H]2OC(C)(C)O[C@H]2O1 KEJGAYKWRDILTF-JDDHQFAOSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- DDCYYCUMAFYDDU-UHFFFAOYSA-N methyl thiohypochlorite Chemical compound CSCl DDCYYCUMAFYDDU-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a styrene monomer containing chiral sulfoxide, which comprises the steps of stirring and reacting bis-ketal glucose and methyl sulfinyl chloride in an organic solvent at-78 ℃ for 1-3 hours, quenching the reaction by using water, extracting an organic phase by using dichloromethane, washing the organic phase by using dilute hydrochloric acid and sodium bicarbonate aqueous solution in sequence, drying the organic phase by using anhydrous sodium sulfate, and finally separating to obtain the bis-ketal glucose containing chiral sulfoxide substitution; reacting bis-ketal glucose containing chiral sulfoxide and (4-vinyl phenyl) magnesium chloride Grignard reagent in toluene at low temperature for 1-3 hours, quenching with saturated ammonium chloride, extracting an organic phase with dichloromethane, drying and separating the organic phase to obtain the 1- (methyl sulfinyl) -4-vinyl benzene high molecular monomer containing chiral sulfoxide.
Description
Technical Field
The invention relates to the technical field of preparation of neutral coordination organic catalysts, in particular to a preparation method for synthesizing a styrene monomer containing chiral methyl sulfoxide by two steps by taking bis-ketal glucose and methyl thionyl chloride as raw materials.
Background
Neutral coordination organic catalysts generally employ uncharged Lewis bases such as N, N-dimethylformamide, pyridine nitroxide, phosphoramide (HMPA), phosphine oxide and sulfoxide. Among them, chiral sulfoxide catalysts are widely used in asymmetric catalytic synthesis of some molecules with important pharmaceutical activities, but in many asymmetric catalysis, chiral sulfoxide catalysts need to use chemical dose (1-3 times equivalent), and are unrecoverable, and have low use efficiency and a certain burden on the environment. In view of this background, there is a need for the preparation of a chiral sulfoxide that can be copolymerized to be supported on a polymer backbone, i.e., a styrene monomer containing a chiral sulfoxide.
Disclosure of Invention
Based on the defects of the prior art, the technical problem solved by the invention is to provide a low-cost, fast and efficient method for preparing styrene monomers containing chiral methyl sulfoxide, wherein the monomers can be copolymerized into various chiral sulfoxide-containing polymers in future, and the chiral sulfoxide-containing polymers can be used as chiral sulfoxide neutral ligand organic catalysts which can be repeatedly used and can also be loaded in microchannels to realize efficient mobile phase reaction.
In order to solve the above technical problems, the present invention provides a method for preparing a styrene monomer containing chiral sulfoxide, comprising the following steps:
stirring and reacting the bisketal glucose and methylsulfinylchloride in an organic solvent at-78 ℃ for 1-3 hours; after the reaction is finished, quenching the reaction by using water, extracting an organic phase by using dichloromethane, washing the organic phase by using dilute hydrochloric acid with the mass fraction of 5% and a sodium bicarbonate aqueous solution with the mass fraction of 2%, drying the organic phase by using anhydrous sodium sulfate, concentrating the organic phase, and performing column chromatography separation to obtain the bisketal glucose containing chiral sulfoxide substitution; reacting bis-ketal glucose containing chiral sulfoxide and (4-vinylphenyl) magnesium chloride Grignard reagent in toluene at a low temperature of 0-5 ℃ for 1-3 hours, quenching with saturated ammonium chloride, extracting an organic phase with dichloromethane, and drying and separating the organic phase to obtain a 1- (methylsulfinyl) -4-vinylbenzene macromolecular monomer containing chiral sulfoxide;
wherein, the structural formula of the styrene monomer containing the chiral sulfoxide is shown as follows (wherein, the sulfoxide can be R type or S type):
the structural formula of the bisketal glucose is as follows:
the structural formula of the methyl sulfinyl chloride is as follows:
the structural formula of the bisketal glucose containing chiral methyl sulfoxide substitution is as follows:
the structural formula of the (4-vinyl phenyl) magnesium chloride Grignard reagent is as follows:
as a preferred aspect of the above technical solution, the preparation method of the styrene monomer containing chiral sulfoxide provided by the present invention further includes part or all of the following technical features:
as an improvement of the technical scheme, the organic solvent is a mixed solvent of pyridine/tetrahydrofuran and toluene/diisopropylethylamine.
As an improvement of the technical scheme, the molar ratio of the diacetone glucose to the methyl sulfenyl chloride is 1: 1-3.
As an improvement of the technical scheme, the molar ratio of the chiral sulfoxide-containing glucose compound to the (4-vinylphenyl) magnesium chloride Grignard reagent is 1: 1.5-3.
As an improvement of the technical scheme, the bis-ketal glucose and the methylsulfinylchloride are stirred and reacted for 1 to 3 hours in a tetrahydrofuran/pyridine mixed organic solvent at a temperature of minus 78 ℃. And after the reaction is finished, quenching the reaction by using water, extracting an organic phase by using dichloromethane, washing by using dilute hydrochloric acid and dilute sodium bicarbonate aqueous solution, drying the organic phase by using anhydrous sodium sulfate, and finally separating to obtain the R-configuration glucose containing the chiral methyl sulfoxide substituted bisketal.
As an improvement of the technical scheme, the bis-ketal glucose and the methylsulfinylchloride are stirred and reacted for 1 to 3 hours at a temperature of minus 78 ℃ in a mixed organic solvent of toluene/diisopropylethylamine; and after the reaction is finished, quenching the reaction by using water, extracting an organic phase by using dichloromethane, washing by using dilute hydrochloric acid and dilute sodium bicarbonate aqueous solution, drying the organic phase by using anhydrous sodium sulfate, and finally separating to obtain the chiral methyl sulfoxide substituted bisketal glucose with the S configuration.
As an improvement of the technical scheme, the R-type or S-type chiral sulfoxide substituted bis-ketal glucose and the (4-vinylphenyl) magnesium chloride Grignard reagent react in toluene at a low temperature of 0-5 ℃ for 1-3 hours, are quenched by saturated ammonium chloride and subjected to subsequent treatment, and then the 1- (methylsulfinyl) -4-vinylbenzene high molecular monomer containing the chiral sulfoxide (the highest ee value can reach 98%) is obtained through column chromatographic separation.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects: the method for synthesizing the styrene monomer containing the chiral methyl sulfoxide (R type and S type) by using the bis-ketal glucose and the methylsulfonyl chloride as raw materials has the advantages of easily available raw materials, short synthetic route, simple process operation, easy industrial production, low production cost and higher ee value (the highest ee value can reach 98 percent) of the obtained chiral methyl sulfoxide.
1. The sulfoxide synthesis scheme of the conventional process usually uses a strong oxidant and has low yield. Importantly, no literature report on the scheme for synthesizing the styrene monomer containing chiral methyl sulfoxide is found.
2. The preparation process of the styrene monomer containing chiral methyl sulfoxide adopts bisketal glucose and methyl sulfinyl chloride as raw materials, and can obtain R-type or S-type chiral sulfoxide substituted bisketal glucose by reacting in conventional pyridine/tetrahydrofuran or toluene/diisopropylethylamine and other organic solvents, and the subsequent reaction with a (4-vinyl phenyl) magnesium chloride Grignard reagent prepared on site can efficiently obtain the 1- (methyl sulfinyl) -4-vinyl benzene high molecular monomer containing chiral sulfoxide (the highest ee value can reach 98%). The method has the advantages of cheap and easily-obtained raw materials, simple and convenient operation, excellent yield and high ee value of the obtained chiral sulfoxide. The monomers can be copolymerized into various chiral sulfoxide-containing polymers in future, and the chiral sulfoxide-containing polymers can be used as a reusable chiral sulfoxide neutral ligand organic catalyst and can also be loaded in a microchannel to realize efficient fluid phase reaction, so that the method has important academic value and application prospect.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention may be implemented in accordance with the contents of the description, and in order to make the above and other objects, features, and advantages of the present invention more clearly understood, the following detailed description is given in conjunction with the preferred embodiments.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings of the embodiments will be briefly described below.
FIG. 1 shows the synthesis of R-configuration styrene monomer containing chiral methyl sulfoxide in example 1 of the invention1H NMR characterization spectrum;
FIG. 2 shows the synthesis of R-configuration styrene monomer containing chiral methyl sulfoxide in example 113C NMR characterization spectrum;
FIG. 3 shows the synthesis of S-configuration chiral methyl sulfoxide-containing styrene monomer in example 2 of the invention1H NMR characterization spectrum;
FIG. 4 shows the S-configuration chiral methyl sulfoxide-containing styrene monomer synthesized in example 2 of the invention13C NMR characterization spectrum.
Detailed Description
Other aspects, features and advantages of the present invention will become apparent from the following detailed description, which, when taken in conjunction with the drawings, illustrate by way of example the principles of the invention.
EXAMPLE 1 Synthesis of R-configuration chiral methyl sulfoxide-containing styrene monomer
The bisketal glucose (12mmol) and pyridine (14mmol) are added into a reaction bottle, 10mL of tetrahydrofuran is added, the mixed solution is cooled to-78 ℃, methyl thionyl chloride (30mmol) dissolved in 15mL of tetrahydrofuran is slowly added dropwise into the reaction solution, the mixed solution reacts for 2 hours at-78 ℃, and then the reaction solution slowly rises to room temperature. After the reaction was completed, the reaction was quenched with water, the organic phase was extracted with dichloromethane, washed with hydrochloric acid (5%) and sodium bicarbonate (2%), and dried over anhydrous sodium sulfate to give a white solid R-configuration chiral sulfoxide substituted bisketal glucose. To a reaction flask which had been dried in advance and filled with nitrogen (or argon), 5mL of toluene was added, the mixture was cooled to 0 ℃, and then the chiral sulfoxide-substituted bisketal glucose (5mmol) in the R configuration described above was added, and then (4-vinylphenyl) magnesium chloride Grignard reagent (10mmol) was slowly added dropwise to the reaction solution, and the progress of the reaction was monitored by gas chromatography, and after about 1 hour, the exchange reaction was terminated. Then slowly heating the reaction liquid to room temperature, quenching the reaction by using saturated ammonium chloride, extracting an organic phase by using dichloromethane, drying the organic phase by using anhydrous magnesium sulfate, and concentrating the organic phase to obtain 0.32g (colorless oily liquid) of the chiral sulfoxide-containing (R) -1- (methylsulfinyl) -4-vinyl benzene high-molecular monomer, wherein the yield is 40%, ee: 98% and the purity is more than or equal to 95%. FIG. 1 shows the synthesis of R-configuration styrene monomer containing chiral methyl sulfoxide in example 1 of the invention1H NMR characterization spectrum; FIG. 2 shows the synthesis of R-configuration styrene monomer containing chiral methyl sulfoxide in example 113C NMR characterization spectrum.
1H NMR(400MHz,CDCl3):δ(ppm)7.62-7.55(m,4H),6.79-6.72(m,1H),5.86(d,J＝20.0Hz,1H),5.38(d,J＝8.0Hz,1H),2.74(d,J＝4.0Hz,3H).
13C NMR(151MHz,CDCl3):δ(ppm)144.7,140.4,135.6,127.0,123.8,116.2,43.9.
HRMS(ESI)Calcd for C9H10OS(166.0452),found:166.0450.
Example 2 Synthesis of S-configuration chiral methyl sulfoxide-containing styrene monomer
The bisketal glucose (20mmol) and diisopropylethylamine (24mmol) were added to a reaction flask, 24mL of toluene was added, the mixture was cooled to-78 deg.C, methyl thionyl chloride (50mmol) dissolved in 14mL of toluene was slowly added dropwise to the reaction solution, the mixture was reacted at-78 deg.C for 3 hours, and then the reaction solution was slowly warmed to room temperature. After the reaction was completed, the reaction was quenched with water, the organic phase was extracted with dichloromethane, washed with hydrochloric acid (5%) and sodium bicarbonate (2%), and dried over anhydrous sodium sulfate to give a white solid, S-configuration, chiral methyl sulfoxide substituted bisketal glucose. To a reaction flask which had been dried in advance and filled with nitrogen (or argon), 7mL of toluene was added, the mixture was cooled to 0 ℃, followed by addition of the chiral methylsulfoxide-substituted bisketal glucose (7mmol) having the S configuration described above, and then (4-vinylphenyl) magnesium chloride Grignard reagent (14mmol) was slowly added dropwise to the reaction solution, and the progress of the reaction was monitored by gas chromatography, and after about 1 hour, the exchange reaction was terminated. Then slowly raising the reaction liquid to room temperature, quenching the reaction by using saturated ammonium chloride, extracting an organic phase by using ethyl acetate, drying the organic phase by using anhydrous magnesium sulfate, and concentrating the organic phase to obtain 2.47g (colorless oily liquid) of the (S) -1- (methylsulfinyl) -4-vinyl benzene high-molecular monomer containing the chiral methyl sulfoxide, wherein the yield is 54%, ee: 94% and the purity is more than or equal to 95%. FIG. 3 shows the synthesis of S-configuration chiral methyl sulfoxide-containing styrene monomer in example 2 of the invention1H NMR characterization spectrum; FIG. 4 shows the S-configuration chiral methyl sulfoxide-containing styrene monomer synthesized in example 2 of the invention13C NMR characterization spectrum.
1H NMR(500MHz,CDCl3):δ(ppm)7.62-7.55(m,4H),6.78-6.72(m,1H),5.86(d,J＝15Hz,1H),5.38(d,J＝10Hz,1H),2.73(s,3H).
13C NMR(151MHz,CDCl3):δ(ppm)144.7,140.4,135.6,127.0,123.8,116.2,43.9.
HRMS(ESI)Calcd for C9H10OS(166.0452),found:166.0454.
The raw materials listed in the invention, the upper and lower limits and interval values of the raw materials of the invention, and the upper and lower limits and interval values of the process parameters (such as temperature, time and the like) can all realize the invention, and the examples are not listed.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (7)
1. A preparation method of a styrene monomer containing chiral sulfoxide is characterized by comprising the following steps:
stirring and reacting the bisketal glucose and methylsulfinylchloride in an organic solvent at-78 ℃ for 1-3 hours; after the reaction is finished, quenching the reaction by using water, extracting an organic phase by using dichloromethane, washing the organic phase by using dilute hydrochloric acid with the mass fraction of 5% and a sodium bicarbonate aqueous solution with the mass fraction of 2%, drying the organic phase by using anhydrous sodium sulfate, concentrating the organic phase, and separating by using column chromatography to obtain the bisketal glucose containing chiral sulfoxide substitution; reacting bis-ketal glucose containing chiral sulfoxide and (4-vinylphenyl) magnesium chloride Grignard reagent in toluene at a low temperature of 0-5 ℃ for 1-3 hours, quenching with saturated ammonium chloride, extracting an organic phase with dichloromethane, and drying and separating the organic phase to obtain a 1- (methylsulfinyl) -4-vinylbenzene macromolecular monomer containing chiral sulfoxide;
wherein, the structural formula of the styrene monomer containing the chiral sulfoxide is as follows:
the structural formula of the bisketal glucose is as follows:
the structural formula of the methyl sulfinyl chloride is as follows:
the structural formula of the bisketal glucose containing chiral methyl sulfoxide substitution is as follows:
the structural formula of the (4-vinyl phenyl) magnesium chloride Grignard reagent is as follows:
2. the method for preparing a styrene monomer containing chiral sulfoxide according to claim 1, wherein: the organic solvent is a mixed solvent of pyridine/tetrahydrofuran and toluene/diisopropylethylamine.
3. The method for preparing a styrene monomer containing chiral sulfoxide according to claim 1, wherein: the molar ratio of the diacetone glucose to the methyl sulfinyl chloride is 1: 1-3.
4. The method for preparing a styrene monomer containing chiral sulfoxide according to claim 1, wherein: the molar ratio of the glucose compound containing the chiral sulfoxide to the (4-vinyl phenyl) magnesium chloride Grignard reagent is 1: 1.5-3.
5. The method for preparing a styrene monomer containing chiral sulfoxide according to claim 1, wherein: and stirring and reacting the bisketal glucose and methylsulfinylchloride in a tetrahydrofuran/pyridine mixed organic solvent at-78 ℃ for 1-3 hours. And after the reaction is finished, quenching the reaction by using water, extracting an organic phase by using dichloromethane, washing by using dilute hydrochloric acid and dilute sodium bicarbonate aqueous solution, drying the organic phase by using anhydrous sodium sulfate, and finally separating to obtain the R-configuration glucose containing the chiral methyl sulfoxide substituted bisketal.
6. The method for preparing a styrene monomer containing chiral methyl sulfoxide according to claim 1, wherein: stirring and reacting the bisketal glucose and methylsulfinylchloride in a mixed organic solvent of toluene/diisopropylethylamine at-78 ℃ for 1-3 hours; and after the reaction is finished, quenching the reaction by using water, extracting an organic phase by using dichloromethane, washing by using dilute hydrochloric acid and dilute sodium bicarbonate aqueous solution, drying the organic phase by using anhydrous sodium sulfate, and finally separating to obtain the chiral methyl sulfoxide substituted bisketal glucose with the S configuration.
7. The method for preparing a styrene monomer containing chiral methyl sulfoxide according to claim 6-7, wherein: reacting the R-type or S-type chiral sulfoxide substituted bis-ketal glucose with a (4-vinylphenyl) magnesium chloride Grignard reagent in toluene at a low temperature of 0-5 ℃ for 1-3 hours, quenching with saturated ammonium chloride, performing subsequent treatment, and separating by column chromatography to obtain the chiral sulfoxide-containing 1- (methylsulfinyl) -4-vinylbenzene high-molecular monomer.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD222032A1 (en) * | 1984-02-24 | 1985-05-08 | Univ Schiller Jena | PROCESS FOR THE PURIFYING OF SULFONOID GROUP-BASED POLYMERS |
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