CN111068776B - Application of HEH in preparation of sulfone compound by catalyzing reaction of aryl halogen and aryl sulfinate - Google Patents

Application of HEH in preparation of sulfone compound by catalyzing reaction of aryl halogen and aryl sulfinate Download PDF

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CN111068776B
CN111068776B CN202010049250.XA CN202010049250A CN111068776B CN 111068776 B CN111068776 B CN 111068776B CN 202010049250 A CN202010049250 A CN 202010049250A CN 111068776 B CN111068776 B CN 111068776B
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李红喜
朱大亮
钟胜奎
李海燕
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
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    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B45/00—Formation or introduction of functional groups containing sulfur
    • C07B45/04—Formation or introduction of functional groups containing sulfur of sulfonyl or sulfinyl groups
    • C—CHEMISTRY; METALLURGY
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    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
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Abstract

The invention discloses application of diethyl 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylate as a visible light reduction catalyst to preparation of sulfone compounds by inducing non-transition metal catalysis of aryl halogen and aryl sulfinate. Specifically, the method comprises the following steps: under the protection of inert gas, according to the molar ratio of the aryl halogen compound to the sulfinate compound to the inorganic base to HEH of 1:2:1.5:0.2, adding the reactants into a reaction container equipped with a stirring device, adding dimethyl sulfoxide, irradiating by a blue LED, and stirring and reacting for 24 hours at room temperature to obtain the sulfone compound. According to the invention, a series of cross coupling reactions of aryl halogen and sulfinate are realized by taking HEH as a catalyst under the condition of not adding any auxiliary transition metal catalyst for the first time. In addition, the whole process is green, efficient and easy to operate, and the method is a good method for synthesizing the sulfone compound.

Description

Application of HEH in preparation of sulfone compound by catalyzing reaction of aryl halogen and aryl sulfinate
Technical Field
The invention belongs to the technical field of catalytic chemistry, and particularly relates to application of diethyl 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylate (HEH) as a visible light reduction catalyst to preparation of sulfone compounds by inducing non-transition metal catalysis of aryl halogen and aryl sulfinate.
Background
Sulfone compounds are not only important organic complexes, but also widely exist in natural products, bioactive substances and drug molecules. To synthesize such compounds, various methods have been developed. For example, at higher temperatures, the cross-coupling reaction of aryl halides and sulfinates is catalyzed by palladium or copper; a few subject groups realize the cross-coupling reaction of aryl halogen and sulfinate by taking a ruthenium or iridium noble metal complex as a photosensitizer and combining with a nickel catalyst. However, these methods require the combination of expensive Ir/Ru organometallic complexes and transition metal catalysts, which not only increases the cost but also involves the risk of toxicity; in addition, the high-energy ultraviolet light is incompatible with the functional groups and causes side effects.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a brand-new 2, 6-dimethyl-1, 4-dihydro-3, 5-diethyl pyridinedicarboxylate (HEH) catalytic system, and realizes the synthesis of sulfone compounds. Under the condition that no auxiliary transition metal catalyst is added, HEH is used as a catalyst, cesium carbonate is used as alkali, and under the irradiation of a blue LED, a series of cross-coupling reactions of aryl halogen and sulfinate are realized, so that the problem that the arylation reaction of an arylation reagent and sulfinate cannot be induced by visible light due to high reduction potential in the prior art is solved. In addition, the invention can obtain the sulfone compound with higher yield. The whole catalysis process is green, efficient and easy to operate, and is a good method for synthesizing the sulfone compound.
Specifically, the invention adopts the following technical scheme:
application of 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylic acid diethyl ester in catalyzing aryl halogen to react with aryl sulfinate to prepare sulfone compounds.
A method for preparing sulfone compounds takes 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylic diethyl ester as a catalyst, and aryl halogen and aryl sulfinate as raw materials to react to prepare the sulfone compounds.
In the invention, the reaction is carried out for 24 hours under the irradiation of a blue LED at room temperature.
In the invention, the reaction is carried out in a solvent in the presence of alkali under the protection of inert gas; the dosage of the diethyl 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylate is 20 percent of the molar quantity of aryl halogen; preferably, the molar ratio of aryl halogen, aryl sulfinic acid, base is 1:2: 1.5.
The reaction of the invention is carried out in the absence of a metal catalyst or a transition metal catalyst, and the problem that an auxiliary (transition) metal catalyst is needed in the prior art is effectively solved.
In the invention, the aryl halogen has a general structural formula shown in any one of a formula (B) to a formula (E):
Figure 648154DEST_PATH_IMAGE001
wherein: r 1 Selected from cyano, carbonyl, carbomethoxy, nitro, aldehyde, phenyl, methyl or methoxy; x is selected from chlorine, bromine or iodine; r 2 Selected from cyano or benzoyl;
the aryl sulfinate has a general structural formula shown in any one of formulas (H) to (J):
Figure 172676DEST_PATH_IMAGE002
wherein: r 3 Selected from hydrogen, fluoro, trifluoromethyl, methyl, phenyl, tert-butyl or methoxy; r 4 Selected from trifluoromethyl or methyl.
The invention discloses an application of HEH as a visible light reduction catalyst to prepare sulfone compounds by inducing non-transition metal catalysis of aryl halogen and aryl sulfinate, which comprises the following steps: under the protection of inert gas, according to the molar ratio of aryl halogen, aryl sulfinate, inorganic base and HEH =1:2:1.5:0.2, adding the reactants into a reaction container with a stirring device, adding dimethyl sulfoxide, and stirring and reacting for 24 hours at room temperature under the irradiation of a blue LED to obtain the sulfone compound.
In the present invention, the inert gas is selected from any one of nitrogen, helium, neon and argon, preferably nitrogen; the alkali is any one of inorganic alkali, the inorganic alkali is any one of cesium carbonate, sodium carbonate, potassium phosphate, dipotassium hydrogen phosphate and sodium acetate, and cesium carbonate is preferred.
In the invention, the catalyst HEH has a structural formula shown in a formula (I):
Figure 205967DEST_PATH_IMAGE003
in the invention, the halogen site in the aryl halogen reacts with the sulfinic acid site of the sulfinate to prepare the sulfone compound, and the reaction is clear.
Preferably, in the synthesis method of the sulfone compound, the stirring device is a magnetic stirring device.
Preferably, in the above method for synthesizing a sulfone compound, the reaction vessel is a sealed reaction tube.
Preferably, in the synthesis method of the sulfone compound, the reaction is carried out at room temperature under a blue LED (wavelength of 460-485 nm).
Preferably, in the above method for synthesizing a sulfone compound, the reaction time is 24 hours.
Compared with the prior art, the invention adopting the technical scheme has the following advantages: according to the invention, a series of cross coupling reactions of aryl halogen and sulfinate are realized under the irradiation of a blue LED by taking HEH as a catalyst and cesium carbonate as alkali without adding any auxiliary transition metal catalyst for the first time. In addition, the invention can obtain the sulfone compound with higher yield. The whole process is green, efficient and easy to operate, and is a good method for synthesizing the sulfone compounds.
Detailed Description
The invention will be further described with reference to specific embodiments. Unless otherwise indicated, reagents, materials, instruments and the like used in the following examples are commercially available. The reaction of the invention is carried out in the absence of metal catalysts or transition metal catalysts, and only aryl halogen, aryl sulfinate, inorganic base, HEH and DMSO are used as raw materials; the reaction of the embodiment of the invention is carried out at room temperature, and the wavelength of the blue LED is 460-485 nm and 10W.
Example 1: the HEH catalytic system catalyzes the reaction of 4-cyano halogenobenzene and sodium benzene sulfinate.
Figure 677399DEST_PATH_IMAGE004
4-Cyanohalobenzene (X = Cl, Br, Cl, 0.2 mmol), sodium benzenesulfonate (0.4 mmol), Cs 2 CO 3 (0.3 mmol), HEH (20 mol%, 0.04 mmol) and DMSO (1 mL) were added to a dry reaction tube with a magnetic stirrer, which was then used with a N-tube 2 The mixture was replaced 3 times, and the mixture was stirred under blue LED irradiation for 24 hours. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to silica gel chromatography to obtain the target product (X = I, yield 95%; X = Br, yield 92%; X = Cl, yield 83%).
1 H-NMR (400 MHz, CDCl 3 , ppm): δ 8.05 (d, J = 7.9 Hz, 2H), 7.95 (d, J = 7.7 Hz, 2H), 7.80 (d, J = 8.0 Hz, 2H), 7.63 (t, J = 7.1 Hz, 1H), 7.55 (t, J = 7.5 Hz, 2H)； 13 C-NMR (101 MHz, CDCl 3 , ppm): δ 146.1, 140.4, 134.2, 133.3, 129.9, 128.5, 128.2, 117.3, 117.2。
Example 2: the HEH catalytic system catalyzes 4-acetylbromobenzene to react with sodium benzene sulfinate.
Figure 731943DEST_PATH_IMAGE005
4-acetyl bromobenzene (0.2 mmol), sodium benzene sulfinate (0.4 mmol) and Cs 2 CO 3 (0.3 mmol), HEH (20 mol%) and DMSO (1 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N 2 Replacing for 3 times, and stirring under the irradiation of blue LEDStirring and reacting for 24 h. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to silica gel chromatography to obtain the desired product (yield 91%). Cs 2 CO 3 Potassium carbonate was substituted and the remainder was not changed to obtain the objective product (yield 90%).
1 H-NMR (400 MHz, CDCl 3 , ppm): δ 8.09–8.01 (m, 4H), 7.96 (d, J = 7.5 Hz, 2H), 7.60 (t, J = 7.3 Hz, 1H), 7.53 (t, J = 7.5 Hz, 2H), 2.62 (s, 3H)。
13 C-NMR (101 MHz, CDCl 3 , ppm): δ 196.8, 145.7, 141.1, 140.6, 133.8, 129.7, 129.3, 128.2, 128.1, 27.1。
Example 3: the HEH catalytic system catalyzes the reaction of the 4-bromobenzoate and the benzene sulfinic acid sodium.
Figure 692946DEST_PATH_IMAGE006
4-bromobenzoic acid methyl ester (0.2 mmol), sodium benzene sulfinate (0.4 mmol), Cs 2 CO 3 (0.3 mmol), HEH (20 mol%) and DMSO (1 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N 2 The displacement is carried out for 3 times, and the reaction is stirred for 24 hours under the irradiation of a blue LED. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to silica gel chromatography to obtain the desired product (yield 91%).
1 H-NMR (400 MHz, CDCl 3 , ppm): δ 8.15 (d, J = 8.3 Hz, 2H), 8.02 (d, J = 8.3 Hz, 2H), 7.96 (d, J = 7.6 Hz, 2H), 7.60 (t, J = 7.2 Hz, 1H), 7.53 (t, J = 7.5 Hz, 2H), 3.94 (s, 3H)。
13 C-NMR (101 MHz, CDCl 3 , ppm): δ 165.7, 145.7, 141.1, 134.5, 133.8, 130.6, 129.6, 128.0, 127.9, 52.8。
Example 4: the HEH catalytic system catalyzes the reaction of 4-ethyl bromobenzoate and sodium benzene sulfinate.
4-Bromobenzoic acid ethyl ester (0.2 mmol), sodium benzene sulfinate (0.4 mmol), Cs 2 CO 3 (0.3 mmol), HEH (20 mol%) and DMSO (1 mL) were added to a dry reaction tube with a magnetic stir bar, followed by N 2 The mixture was replaced 3 times, and the mixture was stirred under blue LED irradiation for 24 hours. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to silica gel chromatography to obtain the desired product (yield 90%).
1 H-NMR (400 MHz, CDCl 3 , ppm): δ 8.15 (d, J = 8.3 Hz, 2H), 8.01 (d, J = 8.3 Hz, 2H), 7.95 (d, J = 7.5 Hz, 2H), 7.59 (t, J = 7.2 Hz, 1H), 7.52 (t, J = 7.5 Hz, 2H), 4.39 (q, J = 7.1 Hz, 2H), 1.38 (t, J = 7.1 Hz, 3H)。
13 C-NMR (101 MHz, CDCl 3 , ppm): δ 165.2, 145.6, 141.2, 134.9, 133.8, 130.6, 129.7, 128.1, 127.9, 61.9, 14.4。
Example 5: the HEH catalytic system catalyzes 4-bromonitrobenzene to react with sodium benzene sulfinate.
4-bromonitrobenzene (0.2 mmol), sodium benzene sulfinate (0.4 mmol), Cs 2 CO 3 (0.3 mmol), HEH (20 mol%) and DMSO (1 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N 2 The displacement is carried out for 3 times, and the reaction is stirred for 24 hours under the irradiation of a blue LED. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to silica gel chromatography to obtain the desired product (yield 73%).
1 H-NMR (400 MHz, CDCl 3 , ppm): δ 8.34 (d, J = 8.7 Hz, 2H), 8.13 (d, J = 8.7 Hz, 2H), 7.97 (d, J = 7.6 Hz, 2H), 7.64 (t, J = 7.3 Hz, 1H), 7.56 (t, J = 7.6 Hz, 2H)。
13 C-NMR (101 MHz, CDCl 3 , ppm): δ 150.6, 147.6, 140.3, 134.3, 129.9, 129.2, 128.3, 124.7。
Example 6: the HEH catalytic system catalyzes 4-bromobenzaldehyde to react with sodium benzene sulfinate.
4-bromobenzaldehyde (0.2 mmol), sodium benzene sulfinate (0.4 mmol) and Cs 2 CO 3 (0.3 mmol), HEH (20 mol%) and DMSO (1 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N 2 The displacement is carried out for 3 times, and the reaction is stirred for 24 hours under the irradiation of a blue LED. After the reaction, 5 mL of water is added, and then the mixture is extracted by 3X 5 mL of ethyl acetate, organic phases are combined, the organic phase is dried by anhydrous sodium sulfate, the organic phase is filtered, and the filtrate is subjected to rotary evaporation and concentration and then is separated by silica gel chromatography to obtain the target product (yield 60%).
1 H-NMR (400 MHz, CDCl 3 , ppm): δ 10.07 (s, 1H), 8.11 (d, J = 8.1 Hz, 2H), 7.99 (dd, J = 13.4 Hz, 7.9 Hz, 4H), 7.61 (t, J = 7.3 Hz, 1H), 7.54 (t, J= 7.5 Hz, 2H)。
13 C-NMR (101 MHz, CDCl 3 , ppm): δ 190.9, 147.0, 140.9, 139.4, 134.0, 130.5, 129.8, 128.6, 128.2。
Example 7: the HEH catalytic system catalyzes 4-bromobiphenyl to react with sodium benzene sulfinate.
Adding 4-bromobiphenyl (0.2 mmol), sodium benzene sulfinate (0.4 mmol) and Cs 2 CO 3 (0.3 mmol), HEH (20 mol%) and DMSO (1 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N 2 The displacement is carried out for 3 times, and the reaction is stirred for 24 hours under the irradiation of a blue LED. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to chromatography on silica gel to obtain the desired product (yield 68%).
1 H-NMR (400 MHz, CDCl 3 , ppm): δ 8.00 (t, J = 7.6 Hz, 4H), 7.70 (d, J = 8.2 Hz, 2H), 7.63 – 7.50 (m, 5H), 7.43 (dt, J = 22.0, 7.0 Hz, 3H)。
13 C-NMR (101 MHz, CDCl 3 , ppm): δ 146.4, 142.0, 140.3, 139.4, 133.4, 129.5, 129.3, 128.8, 128.4, 128.2, 127.9, 127.6。
Example 8: the HEH catalytic system catalyzes 4-methyliodobenzene to react with sodium benzene sulfinate.
4-methyliodobenzene (0.2 mmol), sodium benzene sulfinate (0.4 mmol) and Cs 2 CO 3 (0.3 mmol), HEH (20 mol%) and DMSO (1 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N 2 The displacement is carried out for 3 times, and the reaction is stirred for 24 hours under the irradiation of a blue LED. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to chromatography on silica gel to obtain the desired product (yield 74%). Cs 2 CO 3 Potassium carbonate was substituted and the remainder was not changed to obtain the objective product (yield 76%).
1 H-NMR (400 MHz, CDCl 3 , ppm): δ 7.93 (d, J = 7.4 Hz, 2H), 7.83 (d, J = 8.1 Hz, 2H), 7.58 –7.52 (m, 1H), 7.49 (t, J = 7.3 Hz, 2H), 7.30 (d, J = 8.0 Hz, 2H), 2.40 (s, 3H)。
13 C-NMR (101 MHz, CDCl 3 , ppm): δ 144.4, 142.3, 139.0, 133.2, 130.1, 129.4, 127.9, 127.7, 21.8。
Example 9: the HEH catalytic system catalyzes 4-methoxy iodobenzene to react with sodium benzene sulfinate.
4-methoxy iodobenzene (0.2 mmol), sodium benzene sulfinate (0.4 mmol) and Cs 2 CO 3 (0.3 mmol), HEH (20 mol%) and DMSO (1 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N 2 Replacing 3 times, and stirring and reacting 24 times under the irradiation of a blue LEDh. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to silica gel chromatography to obtain the desired product (yield 65%).
1 H-NMR (400 MHz, CDCl 3 , ppm): δ 7.90 (dd, J = 14.3, 8.0 Hz, 4H), 7.51 (dq, J = 14.2, 7.0 Hz, 3H), 6.97 (d, J = 8.1 Hz, 2H), 3.84 (s, 3H)。
13 C-NMR (101 MHz, CDCl 3 , ppm): δ 163.6, 142.6, 133.4, 133.0, 130.1, 129.4, 127.5, 114.7, 55.9。
Example 10: the HEH catalytic system catalyzes the reaction of 3-bromobenzonitrile and sodium benzene sulfinate.
3-bromobenzonitrile (0.2 mmol), sodium benzene sulfinate (0.4 mmol) and Cs 2 CO 3 (0.3 mmol), HEH (20 mol%) and DMSO (1 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N 2 The mixture was replaced 3 times, and the mixture was stirred under blue LED irradiation for 24 hours. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to chromatography on silica gel to obtain the desired product (yield 63%).
1 H-NMR (400 MHz, CDCl 3 , ppm): δ 8.21 (s, 1H), 8.16 (d, J = 8.0 Hz, 1H), 7.95 (d, J = 7.6 Hz, 2H), 7.83 (d, J = 7.7 Hz, 1H), 7.64 (dd, J = 17.4, 7.7 Hz, 2H), 7.55 (t, J = 7.5 Hz, 2H)。
13 C-NMR (101 MHz, CDCl 3 , ppm): δ 143.7, 140.4, 136.4, 134.2, 131.7, 131.4, 130.6, 129.8, 128.1, 117.1, 114.1。
Example 11: the HEH catalytic system catalyzes the reaction of 2-bromobenzonitrile and sodium benzene sulfinate.
2-bromobenzonitrile (0.2 mmol), sodium benzene sulfinate (0.4 mmol) and Cs 2 CO 3 (0.3 mmol), HEH (20 mol%) andDMSO (1 mL) was added to a dry reaction tube with a magnetic stirrer, followed by N 2 The displacement is carried out for 3 times, and the reaction is stirred for 24 hours under the irradiation of a blue LED. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to silica gel chromatography to obtain the desired product (yield 51%).
1 H-NMR (400 MHz, CDCl 3 , ppm): δ 8.33 (d, J = 7.9 Hz, 1H), 8.07 (d, J = 7.6 Hz, 2H), 7.81 (t, J = 7.1 Hz, 2H), 7.69 (t, J = 7.5 Hz, 1H), 7.63 (t, J = 7.2 Hz, 1H), 7.55 (t, J = 7.5 Hz, 2H)。
13 C-NMR (101 MHz, CDCl 3 , ppm): δ 143.7, 139.6, 135.8, 134.4, 133.6, 133.5, 129.9, 129.6, 128.7, 115.8, 111.4。
Example 12: the HEH catalytic system catalyzes 2-bromobenzophenone to react with sodium benzene sulfinate.
2-bromobenzophenone (0.2 mmol), sodium benzene sulfinate (0.4 mmol) and Cs 2 CO 3 (0.3 mmol), HEH (20 mol%) and DMSO (1 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N 2 The displacement is carried out for 3 times, and the reaction is stirred for 24 hours under the irradiation of a blue LED. After the reaction, 5 mL of water is added, and then the mixture is extracted by 3X 5 mL of ethyl acetate, organic phases are combined, the organic phase is dried by anhydrous sodium sulfate, the organic phase is filtered, and the filtrate is subjected to rotary evaporation and concentration and then is separated by silica gel chromatography to obtain the target product (yield 63%).
1 H-NMR (400 MHz, CDCl 3 , ppm): δ 8.20 – 8.13 (m, 1H), 7.92 (d, J = 7.6 Hz, 2H), 7.79 (d, J = 7.6 Hz, 2H), 7.64 (dd, J = 5.3, 3.3 Hz, 2H), 7.56 (dd, J = 12.9, 7.0 Hz, 2H), 7.52–7.41 (m, 4H), 7.35–7.29 (m, 1H)。
13 C-NMR (101 MHz, CDCl 3 , ppm): δ 195.9, 141.6, 140.3, 139.9, 137.1, 133.9, 133.5, 133.1, 130.4, 130.4, 130.2, 129.3, 128.7, 128.4, 128.3。
Example 13: the HEH catalytic system catalyzes the reaction of 2-bromonaphthalene and sodium benzene sulfinate.
Mixing 2-bromonaphthalene (0.2 mmol), sodium benzene sulfinate (0.4 mmol), and Cs 2 CO 3 (0.3 mmol), HEH (20 mol%) and DMSO (1 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N 2 The displacement is carried out for 3 times, and the reaction is stirred for 24 hours under the irradiation of a blue LED. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to chromatography on silica gel to obtain the desired product (yield 60%).
1 H-NMR (400 MHz, CDCl 3 , ppm): δ 8.58 (s, 1H), 8.00 (t, J = 7.1 Hz, 3H), 7.93 (d, J = 8.7 Hz, 1H), 7.87 (t, J = 8.8 Hz, 2H), 7.63 (dd, J = 13.8, 6.9 Hz, 2H), 7.57–7.47 (m, 3H)。
13 C-NMR (101 MHz, CDCl 3 , ppm): δ 141.8, 138.6, 135.2, 133.4, 132.4, 129.9, 129.6, 129.5, 129.4, 129.3, 128.1, 127.9, 127.9, 122.9。
Example 15: the HEH catalytic system catalyzes 4-bromobenzonitrile and 4-fluorobenzene sodium sulfinate to react.
4-bromobenzonitrile (0.2 mmol), 4-fluorobenzenesulfonic acid sodium salt (0.4 mmol) and Cs 2 CO 3 (0.3 mmol), HEH (20 mol%) and DMSO (1 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N 2 The mixture was replaced 3 times, and the mixture was stirred under blue LED irradiation for 24 hours. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to silica gel chromatography to obtain the desired product (yield 89%).
1 H-NMR (400 MHz, CDCl 3 , ppm): δ 8.04 (d, J = 8.3 Hz, 2H), 7.97 (dd, J= 8.6, 5.0 Hz, 2H), 7.81 (d, J = 8.3 Hz, 2H), 7.21 (t, J = 8.4 Hz, 2H)。
13 C-NMR (101 MHz, CDCl 3 , ppm): δ 166.1 (d, J = 258.6 Hz), 145.9, 136.4, 136.4, 133.4, 131.1 (d, J = 10.1 Hz), 128.4, 117.3, 117.2 (q, J = 23.2 Hz), 117.2。
Example 16: the HEH catalytic system catalyzes 4-bromobenzonitrile and 4- (trifluoromethyl) benzene sulfinic acid sodium to react.
4-bromobenzonitrile (0.2 mmol), sodium 4- (trifluoromethyl) benzenesulfinate (0.4 mmol) and Cs 2 CO 3 (0.3 mmol), HEH (20 mol%) and DMSO (1 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N 2 The displacement is carried out for 3 times, and the reaction is stirred for 24 hours under the irradiation of a blue LED. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to silica gel chromatography to obtain the desired product (yield 85%).
1 H-NMR (400 MHz, CDCl 3 , ppm): δ 8.08 (dd, J = 8.1, 3.7 Hz, 4H), 7.82 (t, J = 8.5 Hz, 4H)。
13 C-NMR (101 MHz, CDCl 3 , ppm): δ 145.0, 144.0, 135.9 (q, J = 34.3 Hz), 133.5, 128.8, 128.7, 127.0 (q, J = 4.0 Hz), 123.1 (q, J = 273.7 Hz), 117.8, 117.1。
Example 17: the HEH catalytic system catalyzes the reaction of 4-bromobenzonitrile and 4-methyl benzene sulfinic acid sodium.
4-bromobenzonitrile (0.2 mmol), sodium 4-methylbenzenesulfonate (0.4 mmol) and Cs 2 CO 3 (0.3 mmol), HEH (20 mol%) and DMSO (1 mL) were added to a dry reaction tube with a magnetic stir bar, followed by N 2 The mixture was replaced 3 times, and the mixture was stirred under blue LED irradiation for 24 hours. After the reaction is finished, adding 5 mL of water, extracting with 3X 5 mL of ethyl acetate, combining organic phases, drying the organic phase with anhydrous sodium sulfate, filtering, concentrating the filtrate by rotary evaporation, and performing silica gel chromatographyThe desired product was isolated (62% yield).
1 H-NMR (400 MHz, CDCl 3 , ppm): δ 8.03 (d, J = 8.3 Hz, 2H), 7.82 (d, J = 8.1 Hz, 2H), 7.78 (d, J = 8.3 Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H), 2.42 (s, 3H)。
13 C-NMR (101 MHz, CDCl 3 , ppm): δ 146.5, 145.5, 137.3, 133.2, 130.5, 128.3, 128.3, 117.4, 116.9, 21.9。
Example 18: the HEH catalytic system catalyzes 4-bromobenzonitrile and 4-tert-butyl benzene sodium sulfinate to react.
4-bromobenzonitrile (0.2 mmol), sodium 4-tert-butylbenzenesulfonate (0.4 mmol), Cs 2 CO 3 (0.3 mmol), HEH (20 mol%) and DMSO (1 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N 2 The displacement is carried out for 3 times, and the reaction is stirred for 24 hours under the irradiation of a blue LED. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to chromatography on silica gel to obtain the desired product (yield 63%).
1 H-NMR (400 MHz, CDCl 3 , ppm): δ 8.05 (d, J = 8.2 Hz, 2H), 7.85 (d, J = 8.4 Hz, 2H), 7.79 (d, J = 8.3 Hz, 2H), 7.54 (d, J = 8.4 Hz, 2H), 1.31 (s, 9H)。
13 C-NMR (101 MHz, CDCl 3 , ppm): δ 158.4, 146.4, 137.2, 133.2, 128.4, 128.0, 126.9, 117.4, 116.9, 35.5, 31.2。
Example 19: the HEH catalytic system catalyzes 4-bromobenzonitrile to react with 4-methoxybenzene sulfinic acid sodium.
4-bromobenzonitrile (0.2 mmol), sodium 4-methoxybenzenesulfonate (0.4 mmol) and Cs 2 CO 3 (0.3 mmol), HEH (20 mol%) and DMSO (1 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N 2 The displacement is carried out for 3 times, and the reaction is stirred for 24 hours under the irradiation of a blue LED. Reaction junctionAfter completion, 5 mL of water was added, followed by extraction with 3X 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to chromatography on silica gel to obtain the desired product (yield 58%).
1 H-NMR (400 MHz, CDCl 3 , ppm): δ 8.01 (d, J = 8.2 Hz, 2H), 7.87 (d, J = 8.8 Hz, 2H), 7.77 (d, J = 8.2 Hz, 2H), 6.99 (d, J = 8.8 Hz, 2H), 3.85 (s, 3H)。
13 C-NMR (101 MHz, CDCl 3 , ppm): δ 164.2, 146.8, 133.2, 131.5, 130.4, 128.1, 117.4, 116.7, 115.1, 55.9。
Example 20: the HEH catalytic system catalyzes 4-bromobenzonitrile and 3- (trifluoromethyl) benzene sulfinic acid sodium to react.
4-bromobenzonitrile (0.2 mmol), sodium 3- (trifluoromethyl) benzenesulfinate (0.4 mmol) and Cs 2 CO 3 (0.3 mmol), HEH (20 mol%) and DMSO (1 mL) were added to a dry reaction tube with a magnetic stirrer, which was then purged with N 2 The mixture was replaced 3 times, and the mixture was stirred under blue LED irradiation for 24 hours. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to chromatography on silica gel to obtain the desired product (yield 78%).
1 H-NMR (400 MHz, CDCl 3 , ppm): δ 8.21 (s, 1H), 8.14 (d, J = 7.8 Hz, 1H), 8.08 (d, J = 7.5 Hz, 2H), 7.86 (dd, J = 16.8, 7.6 Hz, 3H), 7.71 (t, J = 7.7 Hz, 1H)。
13 C-NMR (101 MHz, CDCl 3 , ppm): δ 145.0, 141.7, 133.5, 132.6 (q, J = 34.3 Hz), 131.5, 130.9 (q, J = 3.0 Hz), 130.8, 128.7, 125.2 (q, J = 4.0 Hz), 123.1 (q, J = 273.7 Hz), 117.8, 117.1。
Example 21: the HEH catalytic system catalyzes 4-bromobenzonitrile and 3, 5-difluorobenzene sodium sulfinate to react.
Reacting 4-bromoBenzonitrile (0.2 mmol), sodium 3, 5-difluorobenzenesulfinate (0.4 mmol), Cs 2 CO 3 (0.3 mmol), HEH (20 mol%) and DMSO (1 mL) were added to a dry reaction tube with a magnetic stir bar, followed by N 2 The displacement is carried out for 3 times, and the reaction is stirred for 24 hours under the irradiation of a blue LED. After the reaction, 5 mL of water was added, followed by extraction with 3 × 5 mL of ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to silica gel chromatography to obtain the desired product (yield 87%).
1 H-NMR (400 MHz, CDCl 3 , ppm): δ 8.06 (d, J = 8.2 Hz, 2H), 7.85 (d, J = 8.2 Hz, 2H), 7.48 (d, J = 3.4 Hz, 2H), 7.07 (t, J = 8.3 Hz, 1H)。
13 C-NMR (101 MHz, CDCl 3 , ppm): δ 163.3 (dd, J = 256.7, 11.4 Hz), 144.7, 143.8 (t, J = 8.1 Hz), 133.6, 128.8, 117.9, 117.1, 111.8 (dd, J = 11.4, 28.6 Hz), 109.9 (t, J = 25.0 Hz)。

Claims (8)

  1. The application of diethyl 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylate in catalyzing the reaction of aryl halogen and aryl sulfinate to prepare sulfone compounds;
    the aryl halogen has a general structural formula shown in any one of formulas (B) to (E):
    Figure 915522DEST_PATH_IMAGE001
    wherein: r 1 Selected from cyano, carbonyl, methyl formate, ethyl formate, nitro, aldehyde, phenyl, methyl or methoxy; x is selected from chlorine, bromine or iodine; r 2 Selected from cyano or benzoyl;
    the reaction is carried out in DMSO in the presence of cesium carbonate under the protection of inert gas; the reaction is carried out at room temperature for 24 hours under the irradiation of a blue LED.
  2. 2. Use according to claim 1, characterized in that: the dosage of the diethyl 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylate is 20 percent of the molar quantity of aryl halogen.
  3. 3. Use according to claim 1, characterized in that: the molar ratio of aryl halogen, aryl sulfinate and cesium carbonate is 1:2: 1.5.
  4. 4. Use according to claim 1, characterized in that: the aryl sulfinate has a general structural formula shown in any one of a formula (H) to a formula (J):
    Figure 176739DEST_PATH_IMAGE002
    wherein: r 3 Selected from hydrogen, fluoro, trifluoromethyl, methyl, phenyl, tert-butyl or methoxy; r 4 Selected from trifluoromethyl or methyl.
  5. 5. The method for preparing the sulfone compound is characterized in that 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylic diethyl ester is taken as a catalyst, and aryl halogen and aryl sulfinate are taken as raw materials to react to prepare the sulfone compound; the aryl halogen has a general structural formula shown in any one of a formula (B) to a formula (E):
    Figure 148413DEST_PATH_IMAGE001
    wherein: r 1 Selected from cyano, carbonyl, carbomethoxy, nitro, aldehyde, phenyl, methyl or methoxy; x is selected from chlorine, bromine or iodine; r is 2 Selected from cyano or benzoyl;
    the reaction is carried out in DMSO in the presence of cesium carbonate under the protection of inert gas; the reaction is carried out at room temperature for 24 hours under the irradiation of a blue LED.
  6. 6. The method for producing a sulfone compound according to claim 5, characterized in that: the dosage of the diethyl 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylate is 20 percent of the molar quantity of aryl halogen.
  7. 7. The method for producing a sulfone compound according to claim 5, characterized in that: the molar ratio of the aryl halogen to the aryl sulfinate to the cesium carbonate is 1:2: 1.5.
  8. 8. The method for producing a sulfone compound according to claim 5, characterized in that: the aryl sulfinate has a general structural formula shown in any one of a formula (H) to a formula (J):
    Figure 672936DEST_PATH_IMAGE002
    wherein: r 3 Selected from hydrogen, fluoro, trifluoromethyl, methyl, phenyl, tert-butyl or methoxy; r 4 Selected from trifluoromethyl or methyl.
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