CN109824558B - Method for preparing diphenyl sulfone compound under catalysis of palladium acetate - Google Patents
Method for preparing diphenyl sulfone compound under catalysis of palladium acetate Download PDFInfo
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- CN109824558B CN109824558B CN201910068333.0A CN201910068333A CN109824558B CN 109824558 B CN109824558 B CN 109824558B CN 201910068333 A CN201910068333 A CN 201910068333A CN 109824558 B CN109824558 B CN 109824558B
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- -1 diphenyl sulfone compound Chemical class 0.000 title claims abstract description 46
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 title claims abstract description 45
- KZTYYGOKRVBIMI-UHFFFAOYSA-N S-phenyl benzenesulfonothioate Natural products C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 19
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical group [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910000024 caesium carbonate Inorganic materials 0.000 claims abstract description 18
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 18
- 239000000376 reactant Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 150000004768 bromobenzenes Chemical class 0.000 claims abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims abstract description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 claims abstract description 3
- 150000001558 benzoic acid derivatives Chemical class 0.000 claims abstract description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 3
- 239000012429 reaction media Substances 0.000 claims abstract description 3
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 57
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 13
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 11
- 239000005711 Benzoic acid Substances 0.000 claims description 9
- 235000010233 benzoic acid Nutrition 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- QARVLSVVCXYDNA-UHFFFAOYSA-N phenyl bromide Natural products BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 238000004587 chromatography analysis Methods 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000001559 benzoic acids Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 48
- 238000005160 1H NMR spectroscopy Methods 0.000 description 24
- 239000007832 Na2SO4 Substances 0.000 description 13
- 238000001816 cooling Methods 0.000 description 13
- 238000010898 silica gel chromatography Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 12
- 239000012074 organic phase Substances 0.000 description 12
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 12
- 229920006395 saturated elastomer Polymers 0.000 description 12
- 239000011780 sodium chloride Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 12
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- GPVDHNVGGIAOQT-UHFFFAOYSA-N Veratric acid Natural products COC1=CC=C(C(O)=O)C(OC)=C1 GPVDHNVGGIAOQT-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- WZRKSPFYXUXINF-UHFFFAOYSA-N 1-(bromomethyl)-4-methylbenzene Chemical compound CC1=CC=C(CBr)C=C1 WZRKSPFYXUXINF-UHFFFAOYSA-N 0.000 description 2
- XHQZJYCNDZAGLW-UHFFFAOYSA-N 3-methoxybenzoic acid Chemical compound COC1=CC=CC(C(O)=O)=C1 XHQZJYCNDZAGLW-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZAEYHZCHTBPWHA-UHFFFAOYSA-N 1,2,3-trimethoxy-4-(4-methylphenyl)sulfonylbenzene Chemical compound COC1=CC=C(C(OC)=C1OC)S(=O)(=O)C1=CC=C(C)C=C1 ZAEYHZCHTBPWHA-UHFFFAOYSA-N 0.000 description 1
- RSRGKRWYLIXOBN-UHFFFAOYSA-N 1,2-dimethoxy-4-(4-methylphenyl)sulfonylbenzene Chemical compound C1=C(OC)C(OC)=CC=C1S(=O)(=O)C1=CC=C(C)C=C1 RSRGKRWYLIXOBN-UHFFFAOYSA-N 0.000 description 1
- ITAJGXLAYACITF-UHFFFAOYSA-N 1-methyl-2-(4-methylphenyl)sulfonylbenzene Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C1=CC=CC=C1C ITAJGXLAYACITF-UHFFFAOYSA-N 0.000 description 1
- HZNQSWJZTWOTKM-UHFFFAOYSA-N 2,3,4-trimethoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C(OC)=C1OC HZNQSWJZTWOTKM-UHFFFAOYSA-N 0.000 description 1
- DAUAQNGYDSHRET-UHFFFAOYSA-N 3,4-dimethoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1OC DAUAQNGYDSHRET-UHFFFAOYSA-N 0.000 description 1
- RATSANVPHHXDCT-UHFFFAOYSA-N 4-(trifluoromethoxy)benzoic acid Chemical compound OC(=O)C1=CC=C(OC(F)(F)F)C=C1 RATSANVPHHXDCT-UHFFFAOYSA-N 0.000 description 1
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 1
- NNJMFJSKMRYHSR-UHFFFAOYSA-N 4-phenylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=CC=C1 NNJMFJSKMRYHSR-UHFFFAOYSA-N 0.000 description 1
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 1
- QJLNJMFJSRRBBS-UHFFFAOYSA-N COC1=CC(OC)=CC=C1S(=O)(=O)C1=CC=C(C)C=C1 Chemical compound COC1=CC(OC)=CC=C1S(=O)(=O)C1=CC=C(C)C=C1 QJLNJMFJSRRBBS-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ILUJQPXNXACGAN-UHFFFAOYSA-N O-methylsalicylic acid Chemical compound COC1=CC=CC=C1C(O)=O ILUJQPXNXACGAN-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006452 multicomponent reaction Methods 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for preparing a diphenyl sulfone compound shown in a formula (III) by palladium acetate catalysis, which comprises the following steps: the method comprises the following steps of (1) fully reacting bromobenzene compounds shown in formula (I), sodium sulfate and benzoic acid compounds shown in formula (II) in a reaction medium taking dimethyl formamide (DMF) as a solvent under the action of palladium acetate as a catalyst and alkali carbonate as alkali to prepare reactants, and carrying out post-treatment on the reactants to prepare diphenyl sulfone compounds; the catalyst is 20mol% equivalent of palladium acetate, and the alkali metal carbonate is cesium carbonate;
in the reaction formula R1Selected from one of the following: hydrogen, methyl; r2Selected from one of the following: hydrogen, methyl, methoxy, trifluoromethoxy; the raw materials are simple and easy to obtain, and the preparation conditions are mild; the cost is low, and the requirement on equipment is low; the post-treatment is convenient; the catalytic system has wide adaptability and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of chemical intermediate preparation, and particularly relates to a method for preparing a diphenyl sulfone compound by using palladium acetate as a catalyst.
Background
The diphenyl sulfone compounds are important chemical synthesis intermediates, and have wide and important application in the fields of synthesis industry and material industry. The known preparation method of diphenyl sulfone is mainly obtained by transition metal catalysis, such as Pd, Pt and other catalytic benzene and benzenesulfonic acid, and through sulfonation, coupling and hydrolysis, and has the defects of multiple reaction steps, low reaction efficiency, low reaction application range and the like. The method adopts the palladium acetate with high catalytic activity as the catalyst, realizes the high-efficiency preparation of the diphenyl sulfone compound by a multi-component reaction one-pot method, has the advantages of low cost, simple and easily obtained raw materials, wide application range and excellent yield, and has important application prospect in the related pharmaceutical intermediate synthesis industrial field.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a method for preparing a diphenyl sulfone compound under the catalysis of palladium acetate.
The invention is realized by the following technical scheme:
the method for preparing the diphenyl sulfone compound shown in the formula (III) by palladium acetate catalysis is characterized by comprising the following steps: the method comprises the following steps of (1) fully reacting bromobenzene compounds shown in formula (I), sodium sulfate and benzoic acid compounds shown in formula (II) in a reaction medium taking dimethyl formamide (DMF) as a solvent under the action of palladium acetate as a catalyst and alkali carbonate as alkali to obtain reactants, and carrying out post-treatment on the reactants to obtain diphenyl sulfone compounds; the catalyst is 20mol% equivalent of palladium acetate, and the alkali metal carbonate is cesium carbonate;
in the reaction formula R1Selected from one of the following: hydrogen, methyl; r2Selected from one of the following: hydrogen, methyl, methoxy, trifluoromethoxy.
The method for preparing the diphenyl sulfone compound under the catalysis of palladium acetate is characterized in that the ratio of the bromobenzene compound, the benzoic acid compound 3 and the solvent DMF is 3mmol/3mmol/10 mL.
The method for preparing the diphenyl sulfone compound under the catalysis of palladium acetate is characterized in that the ratio of the bromobenzene compound, the benzoic acid compound and cesium carbonate is 3mmol/3mmol/6 mmol.
The method for preparing the diphenyl sulfone compound by the catalysis of palladium acetate is characterized in that the ratio of the bromobenzene compound, the benzoic acid compound and the palladium acetate is 3mmol/3mmol/0.6 mmL.
The method for preparing the diphenyl sulfone compound under the catalysis of palladium acetate is characterized in that the equivalent ratio of the bromobenzene compound, the benzoic acid compound and the sodium sulfate is 1:1:1-1:1: 1.5.
The method for preparing the diphenyl sulfone compound under the catalysis of palladium acetate is characterized in that the reaction temperature is 150 ℃, the reaction time is 12 hours, and the reaction is under the protection of nitrogen.
The method for preparing the diphenyl sulfone compound by the catalysis of palladium acetate is characterized by comprising the following steps:
1) and (3) extraction: after the reactant is cooled to room temperature at normal temperature, 10mL of saturated sodium chloride aqueous solution is added into the reactant, then ethyl acetate is used for extraction for 3 times, 10mL of the saturated sodium chloride aqueous solution is used for each time, and the extraction liquid is combined;
2) concentration: drying the extract with anhydrous sodium sulfate, and rotary drying with rotary evaporator to obtain concentrate;
3) adsorbing the concentrate with column chromatography silica gel, adding into 200-300 mesh chromatography silica gel column, and purifying with n-hexane: and (3) carrying out fast column chromatography on ethyl acetate according to a certain proportion, combining eluent, carrying out spin-drying on a rotary evaporator, and pumping by an oil pump to obtain the product of the diphenyl sulfone compound.
The method for preparing the diphenyl sulfone compound under the catalysis of palladium acetate is characterized in that the drying time in the step 2) is 3 hours.
The method for preparing the diphenyl sulfone compound under the catalysis of palladium acetate is characterized in that the ratio of n-hexane to ethyl acetate in the step 3) is 2:1-3: 1.
The raw materials are simple and easy to obtain, and the preparation conditions are mild; the reaction is carried out under normal pressure and mild temperature, so that the cost is saved, and the requirement on equipment is low; the used solvent DMF and water are mutually soluble, and the post-treatment is convenient; the catalyst system has wide adaptability, and the obtained product has wide application in the fields of chemical industry and material synthesis, is suitable for large-scale industrial production, and has great industrial application prospect.
Drawings
FIG. 1 is a drawing of product 4a of the present invention1H-NMR spectrum;
FIG. 2 shows the product 4b of the present invention1H-NMR spectrum;
FIG. 3 shows the present inventionOf product 4c1H-NMR spectrum;
FIG. 4 shows the product 4d of the present invention1H-NMR spectrum;
FIG. 5 shows the product 4e of the present invention1H-NMR spectrum;
FIG. 6 shows the preparation of 4f according to the invention1H-NMR spectrum;
FIG. 7 shows 4g of the product of the present invention1H-NMR spectrum;
FIG. 8 shows 4h of the product of the present invention1H-NMR spectrum;
FIG. 9 shows the preparation of 4i according to the invention1H-NMR spectrum;
FIG. 10 shows the product 4j of the present invention1H-NMR spectrum;
FIG. 11 shows the preparation of 4k according to the invention1H-NMR spectrum;
FIG. 12 shows 4l of the product of the present invention1H-NMR spectrum.
Detailed Description
The present invention will be described in more detail with reference to specific examples.
The synthesis method comprises the steps of respectively adding 3mmol of bromobenzene compound, 3mmol of benzoic acid compound and 3.6mmol of sodium sulfate into a 25mL round-bottom flask, then sequentially adding 10mL of DMF, 0.6mmol of palladium acetate and 6mmol of cesium carbonate, and reacting at 150 DEG CoStirring is carried out for 12 hours under the condition of C, and the reaction is carried out under the protection of nitrogen. After cooling, 10mL of saturated aqueous NaCl solution was added to the system, extracted 3 times with 10mL of ethyl acetate, the organic phases were combined and washed with anhydrous Na2SO4After drying, evaporating the solvent, and carrying out 200-300-mesh silica gel column chromatography to obtain the pure product of the diphenyl sulfone compound with the yield of 70-95%. Specific examples and characterization data all product structures were determined by comparison of nuclear magnetic resonance and mass spectrometry results as follows.
Example 1: 4a preparation of the product
In a 25mL round-bottomed flask at room temperature were added 513mg (3mmol) of p-methylbromobenzene 1a, 366mg (3mmol) of benzoic acid 3a and 511mg (3.6mmol) of sodium sulfate 2, respectively, followed by addition of 10mL of DMF, 135mg (0.6mmol) of palladium acetate and 1956mg (6mmol) of cesium carbonate in that order at 150 mgoStirring is carried out for 12 hours under the condition of C, and the reaction is carried out under the protection of nitrogen. After cooling, 10mL of saturated aqueous NaCl solution was added to the system, extracted 3 times with 10mL of ethyl acetate, the organic phases were combined and washed with anhydrous Na2SO4After drying, the solvent was distilled off, and the pure p-methyldiphenylsulfone 4a product 543mg by 200-mesh 300-mesh silica gel column chromatography was obtained in 78% yield as a colorless oily liquid. 4a1The H-NMR spectrum is shown in FIG. 1.
1H NMR (400 MHz, CDCl3): 7.35-7.31 (m, 2H), 7.29 (d,J= 4.3 Hz,4H), 7.22 (dd,J= 9.0, 4.3 Hz, 1H), 7.17 (d,J= 7.9 Hz, 2H), 2.37 (s, 3H).
13C NMR (101 MHz, CDCl3): 137.62, 137.14, 132.29, 131.30, 131.07,130.08, 129.80, 129.05, 128.56, 126.42, 21.15.
Example 2: 4b preparation of the product
In a 25mL round-bottomed flask at room temperature were added 513mg (3mmol) of p-methylbromobenzene 1a, 408mg (3mmol) of p-methylbenzoic acid 3b and 511mg (3.6mmol) of sodium sulfate 2, respectively, followed by addition of 10mL of DMF, 135mg (0.6mmol) of palladium acetate and 1956mg (6mmol) of cesium carbonate in that order at 150 mgoStirring is carried out for 12 hours under the condition of C, and the reaction is carried out under the protection of nitrogen. After cooling, 10mL of saturated aqueous NaCl solution was added to the system, extracted 3 times with 10mL of ethyl acetate, the organic phases were combined and washed with anhydrous Na2SO4After drying, evaporating the solvent, and carrying out 200-300-mesh silica gel column chromatography to obtain the di-p-methyl diphenyl sulfone 4b pure 627mg, yield 85%, colorless oily liquid. 4b1The H-NMR spectrum is shown in FIG. 2.
1H NMR (400 MHz, CDCl3): 7.27 (d,J= 7.5 Hz, 2H), 7.26 –7.24 (m,2H), 7.12 (d,J= 8.0 Hz, 4H), 2.35 (s, 6H).
13C NMR (101 MHz, CDCl3): 136.90, 132.67, 131.06, 129.91, 21.07.
Example 3: preparation of 4c product
In a 25mL round-bottomed flask at room temperature were placed 513mg (3mmol) of p-methylbromobenzene 1a, 408mg (3mmol) of o-methylbenzoic acid 3c and 511mg (3.6mmol) of sodium sulfate 2, respectively, followed by addition of 10mL of DMF, 135mg (0.6mmol) of palladium acetate and 1956mg (6mmol) of cesium carbonate in that order at 150 mg (150 mmol)oStirring is carried out for 12 hours under the condition of C, and the reaction is carried out under the protection of nitrogen. After cooling, 10mL of saturated aqueous NaCl solution was added to the system, extracted 3 times with 10mL of ethyl acetate, the organic phases were combined and washed with anhydrous Na2SO4After drying, the solvent was distilled off, and 200-mesh 300-mesh silica gel column chromatography was carried out to give 597mg of a pure p-tolyl-o-tolylsulfone 4c in 81% yield as a colorless oily liquid. 4c1The H-NMR spectrum is shown in FIG. 3.
1H NMR (400 MHz, CDCl3): 7.30 (t,J= 6.2 Hz, 2H), 7.19 – 7.12 (m,4H), 7.09 (d,J= 7.7 Hz, 1H), 7.04 (d,J= 7.5 Hz, 1H), 2.37 (s, 3H), 2.32(s, 3H).
13C NMR (101 MHz, CDCl3): 138.89, 137.39, 136.61, 132.01, 131.62,130.63, 130.02, 128.91, 127.42, 127.12, 21.31, 21.14.
Example 4: preparation of 4d product
513mg (3mmol) of p-methylbenzyl bromide 1a and 534mg (3mmol) of p-methylbenzyl bromide were added to a 25mL round-bottomed flask at room temperature) P-tert-butylbenzoic acid 3d and 511mg (3.6mmol) of sodium sulfate 2, followed by addition of 10mL of DMF, 135mg (0.6mmol) of palladium acetate and 1956mg (6mmol) of cesium carbonate in that order, at 150oStirring is carried out for 12 hours under the condition of C, and the reaction is carried out under the protection of nitrogen. After cooling, 10mL of saturated aqueous NaCl solution was added to the system, extracted 3 times with 10mL of ethyl acetate, the organic phases were combined and washed with anhydrous Na2SO4After drying, the solvent was distilled off, and the pure p-tolylp-tert-butylphenyl sulfone 4d product 752mg by 200-mesh 300-mesh silica gel column chromatography was obtained in 87% yield as a colorless oily liquid. 4d1The H-NMR spectrum is shown in FIG. 4.
1H NMR (400 MHz, CDCl3): 7.30 (dd,J= 4.4, 2.0 Hz, 1H), 7.28 – 7.25(m, 3H), 7.19 – 7.12 (m, 4H), 2.94 –2.87 (m, 1H), 2.36 (s, 3H), 1.27 (s,3H), 1.25 (s, 3H).
13C NMR (101 MHz, CDCl3): 147.75, 137.04, 133.18, 132.39, 131.41,131.07, 130.75, 129.94, 127.29, 33.75, 23.93, 21.10.
Example 5: preparation of 4e product
In a 25mL round bottom flask at room temperature were added 513mg (3mmol) of p-methylbromobenzene 1a, 594mg (3mmol) of p-phenylbenzoic acid 3e and 511mg (3.6mmol) of sodium sulfate 2, followed by 10mL of DMF, 135mg (0.6mmol) of palladium acetate and 1956mg (6mmol) of cesium carbonate in that order at 150 mgoStirring is carried out for 12 hours under the condition of C, and the reaction is carried out under the protection of nitrogen. After cooling, 10mL of saturated aqueous NaCl solution was added to the system, extracted 3 times with 10mL of ethyl acetate, the organic phases were combined and washed with anhydrous Na2SO4After drying, the solvent was distilled off, and the pure p-tolyl-p-phenylphenylsulfone 4e product was obtained in 647mg in 70% yield as a colorless oily liquid by 200-mesh 300-mesh silica gel column chromatography. 4e1The H-NMR spectrum is shown in FIG. 5.
1H NMR (400 MHz, CDCl3): 7.62 – 7.57 (m, 2H), 7.55 –7.51 (m, 2H),7.49 – 7.44 (m, 2H), 7.40 – 7.34 (m, 5H), 7.22 – 7.17 (m, 2H), 2.39 (s, 3H).
13CNMR (101 MHz, CDCl3): 140.43, 139.39, 137.75, 136.31, 132.41,131.20, 130.15, 130.07, 128.84, 127.74, 127.39, 126.94, 21.18.
Example 6: preparation of 4f product
In a 25mL round-bottomed flask at room temperature were placed 513mg (3mmol) of p-methylbromobenzene 1a, 456mg (3mmol) of p-methoxybenzoic acid 3f and 511mg (3.6mmol) of sodium sulfate 2, respectively, followed by addition of 10mL of DMF, 135mg (0.6mmol) of palladium acetate and 1956mg (6mmol) of cesium carbonate in that order at 150 mgoStirring is carried out for 12 hours under the condition of C, and the reaction is carried out under the protection of nitrogen. After cooling, 10mL of saturated aqueous NaCl solution was added to the system, extracted 3 times with 10mL of ethyl acetate, the organic phases were combined and washed with anhydrous Na2SO4After drying, the solvent was distilled off, and the pure p-tolyl-p-methoxyphenyl sulfone 4f was obtained in 715 mg in a yield of 91% by 200-mesh silica gel column chromatography as a colorless oily liquid. 4f1The H-NMR spectrum is shown in FIG. 6.
1H NMR (400 MHz, CDCl3): 7.41 – 7.36 (m, 2H), 7.17 – 7.14 (m, 2H),7.09 (d,J= 8.0 Hz, 2H), 6.91 – 6.87 (m, 2H), 3.83 (s, 3H), 2.33 (s, 3H).
13C NMR (101 MHz, CDCl3): 159.46, 136.14, 134.37, 129.78, 129.39,127.75, 125.65, 114.88, 55.37, 21.00.
Example 7: preparation of 4g of product
In a 25mL round-bottomed flask at room temperature were placed 513mg (3mmol) of p-methylbromobenzene 1a, 456mg (3mmol) of m-methoxybenzoic acid 3g and 511mg (3.6mmol) of sodium sulfate 2, respectively, followed by addition of 10mL of DMF, 135mg (0.6mmol) of palladium acetate and 1956mg (6mmol) of cesium carbonate in that order at 150 mgoStirring is carried out for 12 hours under the condition of C, and the reaction is carried out under the protection of nitrogen. After cooling downAdding 10mL saturated NaCl aqueous solution, extracting with ethyl acetate for 3 times (10 mL each time), mixing organic phases, and adding anhydrous Na2SO4After drying, the solvent was distilled off, and 707 mg of a pure p-tolyl-m-methoxyphenyl sulfone 4g, 90% yield and a colorless oily liquid were obtained by 200-mesh 300-mesh silica gel column chromatography. 4g1The H-NMR spectrum is shown in FIG. 7.
1H NMR (400 MHz, CDCl3): 7.35 (d,J= 7.9 Hz, 2H), 7.19 (dd,J=14.4, 7.6 Hz, 3H), 6.91 – 6.79 (m, 2H), 6.75 (d,J= 6.4 Hz, 1H), 3.77 (s,3H), 2.37 (s, 3H).
13C NMR (101 MHz, CDCl3): 160.00, 138.63, 137.84, 132.64, 130.75,130.11, 129.82, 121.76, 114.80, 112.07, 55.26, 21.17.
Example 8: preparation of the 4h product
In a 25mL round-bottomed flask at room temperature were added 513mg (3mmol) of p-methylbromobenzene 1a, 456mg (3mmol) of o-methoxybenzoic acid 3h and 511mg (3.6mmol) of sodium sulfate 2, respectively, followed by addition of 10mL of DMF, 135mg (0.6mmol) of palladium acetate and 1956mg (6mmol) of cesium carbonate in that order at 150 mgoStirring is carried out for 12 hours under the condition of C, and the reaction is carried out under the protection of nitrogen. After cooling, 10mL of saturated aqueous NaCl solution was added to the system, extracted 3 times with 10mL of ethyl acetate, the organic phases were combined and washed with anhydrous Na2SO4After drying, the solvent was distilled off, and the purified p-tolyl-p-methoxyphenyl sulfone was obtained in 699mg in 89% yield as a colorless oily liquid by 200-mesh 300-mesh silica gel column chromatography. 4h1The H-NMR spectrum is shown in FIG. 8.
1H NMR (400 MHz, CDCl3): 7.35 (d,J= 8.1 Hz, 2H), 7.23 – 7.16 (m,3H), 6.96 (dd,J= 7.7, 1.6 Hz, 1H), 6.92 – 6.83 (m, 2H), 3.92 (s, 3H), 2.38(s, 3H).
13C NMR (101 MHz, CDCl3): 156.55, 137.75, 132.98, 130.12, 129.91,129.82, 127.44, 125.73, 121.22, 110.63, 55.89, 21.19.
Example 9: preparation of 4i product
513mg (3mmol) of p-methylbromobenzene 1a, 546mg (3mmol) of 3, 4-dimethoxybenzoic acid 3i and 511mg (3.6mmol) of sodium sulfate 2 were added in a 25mL round-bottomed flask at room temperature, followed by 10mL of DMF, 135mg (0.6mmol) of palladium acetate and 1956mg (6mmol) of cesium carbonate in that order at 150 mgoStirring is carried out for 12 hours under the condition of C, and the reaction is carried out under the protection of nitrogen. After cooling, 10mL of saturated aqueous NaCl solution was added to the system, extracted 3 times with 10mL of ethyl acetate, the organic phases were combined and washed with anhydrous Na2SO4After drying, the solvent was distilled off, and the pure p-tolyl 3, 4-dimethoxyphenylsulfone 4i product 788mg in 90% yield was obtained by 200-mesh 300-mesh silica gel column chromatography. 4i of1The H-NMR spectrum is shown in FIG. 9.
1H NMR (400 MHz, CDCl3): 7.20 – 7.14 (m, 2H), 7.13 – 7.08 (m, 2H),7.03 (dd,J= 8.3, 2.1 Hz, 1H), 6.97 (d,J= 2.1 Hz, 1H), 6.85 (d,J= 8.3Hz, 1H), 3.91 (s, 3H), 3.85 (s, 3H), 2.33 (s, 3H).
13C NMR (101 MHz, CDCl3): 149.35, 149.00, 136.24, 134.06, 129.81,129.36, 125.87, 125.64, 120.84, 115.77, 111.72, 111.31, 55.97, 21.01.
Example 10: preparation of 4j product
513mg (3mmol) of p-methylbromobenzene 1a, 546mg (3mmol) of 2, 4-dimethoxybenzoic acid 3i and 511mg (3.6mmol) of sodium sulfate 2 were added in a 25mL round-bottomed flask at room temperature, followed by addition of 10mL of DMF, 135mg (0.6mmol) of palladium acetate and 1956mg (6mmol) of cesium carbonate in that order at 150 mgoStirring is carried out for 12 hours under the condition of C, and the reaction is carried out under the protection of nitrogen. After cooling, 10mL of saturated aqueous NaCl solution was added to the system, extracted 3 times with 10mL of ethyl acetate, and combinedOrganic phase with anhydrous Na2SO4After drying, the solvent was distilled off, and the pure p-tolyl 2, 4-dimethoxyphenylsulfone 4j product 797 mg in 91% yield as a colorless oily liquid was obtained by 200-mesh 300-mesh silica gel column chromatography. 4j1The H-NMR spectrum is shown in FIG. 10.
1H NMR (400 MHz, CDCl3): 7.26 (d,J= 8.4 Hz, 1H), 7.14 – 7.10 (m,2H), 7.07 (d, J = 8.2 Hz, 2H), 6.53 (d,J= 2.5 Hz, 1H), 6.49 (dd,J= 8.5,2.5 Hz, 1H), 3.84 (s, 6H), 2.32 (s, 3H).
13C NMR (101 MHz, CDCl3): 161.36, 159.79, 135.78, 135.48, 133.38,129.66, 129.01, 113.62, 105.28, 99.20, 55.96, 55.49, 21.00.
Example 11: preparation of 4k product
513mg (3mmol) of p-methylbromobenzene 1a, 636mg (3mmol) of 2,3, 4-trimethoxybenzoic acid 3k and 511mg (3.6mmol) of sodium sulfate 2 were added in a 25mL round-bottomed flask, respectively, at room temperature, followed by addition of 10mL of DMF, 135mg (0.6mmol) of palladium acetate and 1956mg (6mmol) of cesium carbonate in that order at 150 mgoStirring is carried out for 12 hours under the condition of C, and the reaction is carried out under the protection of nitrogen. After cooling, 10mL of saturated aqueous NaCl solution was added to the system, extracted 3 times with 10mL of ethyl acetate, the organic phases were combined and washed with anhydrous Na2SO4After drying, the solvent was distilled off, and the pure p-tolyl 2,3, 4-trimethoxyphenylsulfone 4k product was obtained in 918 mg in 95% yield as a colorless oily liquid by 200-mesh 300-mesh silica gel column chromatography. 4k1The H-NMR spectrum is shown in FIG. 11.
1H NMR (400 MHz, CDCl3): 7.27 (d,J= 8.3 Hz, 2H), 7.15 (d,J= 8.0Hz, 2H), 6.60 (s, 2H), 3.86 (s, 3H), 3.80 (s, 6H), 2.36 (s, 3H).
13C NMR (101 MHz, CDCl3)： 153.55, 137.39, 137.14, 132.29, 130.92,130.75, 129.97, 108.32, 60.92, 56.17, 21.10.
Example 12: preparation of 4l of product
513mg (3mmol) of p-methylbromobenzene 1a, 618mg (3mmol) of p-trifluoromethoxybenzoic acid 3i and 511mg (3.6mmol) of sodium sulfate 2 were added in a 25mL round-bottomed flask, respectively, at room temperature, followed by addition of 10mL of DMF, 135mg (0.6mmol) of palladium acetate and 1956mg (6mmol) of cesium carbonate in that order at 150 mg (150 mmol)oStirring is carried out for 12 hours under the condition of C, and the reaction is carried out under the protection of nitrogen. After cooling, 10mL of saturated aqueous NaCl solution was added to the system, extracted 3 times with 10mL of ethyl acetate, the organic phases were combined and washed with anhydrous Na2SO4After drying, the solvent was distilled off, and purified by 200-mesh 300-mesh silica gel column chromatography to give 702 mg of p-tolylene-p-trifluoromethylphenylsulfone 4l as a colorless oily liquid in 74% yield. 4l1The H-NMR spectrum is shown in FIG. 11.
1H NMR (400 MHz, CDCl3): 7.41 – 7.37(m, 2H), 7.28 – 7.25 (m, 1H),7.22 (d,J= 7.9 Hz, 2H), 7.13 – 7.10 (m, 1H), 7.05 – 6.99 (m, 2H), 2.40 (s,3H).
13C NMR (101 MHz, CDCl3): 149.62, 140.68, 138.83, 133.59, 130.41,129.97, 129.06, 126.48, 120.63, 119.10, 118.08, 21.21。
Claims (9)
1. A method for preparing diphenyl sulfone compound shown in formula (III) by palladium acetate catalysis is characterized in that the preparation method comprises the following steps: the method comprises the following steps of (1) fully reacting bromobenzene compounds shown in formula (I), sodium sulfate and benzoic acid compounds shown in formula (II) in a reaction medium taking dimethyl formamide (DMF) as a solvent under the action of palladium acetate as a catalyst and alkali carbonate as alkali to obtain reactants, and carrying out post-treatment on the reactants to obtain diphenyl sulfone compounds; the catalyst is 20mol% equivalent of palladium acetate, and the alkali metal carbonate is cesium carbonate;
in the reaction formula R1Selected from one of the following: hydrogen, methyl; r2Selected from one of the following: hydrogen, methyl, methoxy, trifluoromethoxy.
2. The method for preparing the diphenyl sulfone compound under the catalysis of the palladium acetate as claimed in claim 1, wherein the ratio of the bromobenzene compound, the benzoic acid compound and the solvent DMF is 3mmol/3mmol/10 mL.
3. The method for preparing the diphenyl sulfone compound under the catalysis of the palladium acetate as claimed in claim 1, wherein the ratio of the bromobenzenes, the benzoates and the cesium carbonate is 3mmol/3mmol/6 mmol.
4. The method for preparing diphenyl sulfone compound under the catalysis of palladium acetate as claimed in claim 1, wherein the ratio of bromobenzene compound, benzoic acid compound and palladium acetate is 3mmol/3mmol/0.6 mmL.
5. The method for preparing the diphenyl sulfone compound under the catalysis of the palladium acetate according to claim 1, wherein the equivalent ratio of the bromobenzene compound, the benzoic acid compound and the sodium sulfate is 1:1:1-1:1: 1.5.
6. The method for preparing the diphenylsulfone compound under the catalysis of palladium acetate according to claim 1, wherein the reaction temperature is 150 ℃, the reaction time is 12 hours, and the reaction is under the protection of nitrogen.
7. The method for preparing the diphenyl sulfone compound under the catalysis of palladium acetate according to claim 1, which is characterized in that the specific method of post-treatment comprises the following steps:
1) and (3) extraction: after the reactant is cooled to room temperature at normal temperature, 10mL of saturated sodium chloride aqueous solution is added into the reactant, then ethyl acetate is used for extraction for 3 times, 10mL of the saturated sodium chloride aqueous solution is used for each time, and the extraction liquid is combined;
2) concentration: drying the extract with anhydrous sodium sulfate, and rotary drying with rotary evaporator to obtain concentrate;
3) adsorbing the concentrate with column chromatography silica gel, adding into 200-300 mesh chromatography silica gel column, and purifying with n-hexane: and (3) carrying out fast column chromatography on ethyl acetate according to a certain proportion, combining eluent, carrying out spin-drying on a rotary evaporator, and pumping by an oil pump to obtain the product of the diphenyl sulfone compound.
8. The method for preparing diphenylsulfone by palladium acetate catalysis as claimed in claim 7, wherein the drying time in step 2) is 3 hours.
9. The method for preparing the diphenyl sulfone compound under the catalysis of the palladium acetate according to claim 7, wherein the ratio of n-hexane to ethyl acetate in the step 3) is 2:1-3: 1.
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