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CN111068776A - 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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CN111068776A
CN111068776A CN202010049250.XA CN202010049250A CN111068776A CN 111068776 A CN111068776 A CN 111068776A CN 202010049250 A CN202010049250 A CN 202010049250A CN 111068776 A CN111068776 A CN 111068776A
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heh
sulfinate
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CN111068776B (en
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李红喜
朱大亮
钟胜奎
李海燕
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Suzhou University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J2231/4294—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using S nucleophiles, e.g. thiols

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Abstract

本发明公开了一种2,6‑二甲基‑1,4‑二氢‑3,5‑吡啶二羧酸二乙酯作为可见光还原催化剂诱导无过渡金属催化芳基卤素与芳基亚磺酸盐制备砜类化合物的应用。具体而言，该方法包括如下步骤：在惰性气体保护下，按照芳基卤素类化合物:亚磺酸盐类化合物:无机碱:HEH之间的摩尔比为1:2:1.5:0.2，将上述反应物加入到配备搅拌装置的反应容器中，再加入二甲亚砜，于蓝色LED照射，室温下搅拌反应24小时，得到砜类化合物。本发明首次在不添加任何辅助过渡金属催化剂的情况下，以HEH作为催化剂，实现了一系列芳基卤素与亚磺酸盐的交叉偶联反应。另外，本发明整个过程绿色、高效且易于操作，是一种合成砜类化合物的好方法。The invention discloses a kind of diethyl 2,6-dimethyl-1,4-dihydro-3,5-pyridinedicarboxylate as a visible light reduction catalyst to induce transition metal-free catalysis of aryl halogen and aryl sulfinic acid Use of salts to prepare sulfones. Specifically, the method includes the following steps: under the protection of an inert gas, according to the molar ratio between aryl halogen compounds: sulfinate compounds: inorganic base: HEH is 1:2:1.5:0.2, the above-mentioned The reactants were added to a reaction vessel equipped with a stirring device, and then dimethyl sulfoxide was added, and irradiated with a blue LED, the reaction was stirred at room temperature for 24 hours to obtain a sulfone compound. The present invention realizes the cross-coupling reaction of a series of aryl halogen and sulfinate for the first time without adding any auxiliary transition metal catalyst and using HEH as a catalyst. In addition, the whole process of the present invention is green, efficient and easy to operate, and is a good method for synthesizing sulfone compounds.

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 transition-metal-free 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, high energy uv light is incompatible with functional groups and can cause 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 catalytic process is green, efficient and easy to operate, and is a good method for synthesizing sulfone compounds.
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 weight of aryl halogen; preferably, the molar ratio of aryl halogen, aryl sulfinic acid, and 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: r1Selected from cyano, carbonyl, carbomethoxy, nitro, aldehyde, phenyl, methyl or methoxy; x is selected from chlorine, bromine or iodine; r2Selected from cyano or benzoyl;
the aryl sulfinate has a general structural formula shown in any one of a formula (H) to a formula (J):
Figure 172676DEST_PATH_IMAGE002
wherein: r3Selected from hydrogen, fluoro, trifluoromethyl, methyl, phenyl, tert-butyl or methoxy; r4Selected from trifluoromethyl or methyl.
The invention discloses an application of HEH as a visible light reduction catalyst to induce transition-metal-free catalysis of aryl halogen and aryl sulfinate to prepare sulfone compounds, 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 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 for the first time without adding any auxiliary transition metal catalyst. 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 presence of no metal catalyst or transition metal catalyst, 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 460-485nm 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), Cs2CO3(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-tube2The 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, 5mL of water was added, followed by extraction with 3 × 5mL of ethyl acetate, the organic phases were combined, 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%).
1H-NMR (400 MHz, CDCl3, 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)；13C-NMR (101 MHz, CDCl3, 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-acetylbromobenzene (0.2 mmol), sodium benzene sulfinate (0.4 mmol) and Cs2CO3(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 N2The 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, 5mL of water was added, followed by extraction with 3 × 5mL 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%). Cs2CO3Potassium carbonate was substituted and the remainder was unchanged to give the desired product (yield 90%).
1H-NMR (400 MHz, CDCl3, ppm): δ 8.09–8.01 (m, 4H), 7.96 (d,J= 7.5Hz, 2H), 7.60 (t,J= 7.3 Hz, 1H), 7.53 (t,J= 7.5 Hz, 2H), 2.62 (s, 3H)。
13C-NMR (101 MHz, CDCl3, 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), Cs2CO3(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 N2The 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, 5mL of water was added, followed by extraction with 3 × 5mL 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%).
1H-NMR (400 MHz, CDCl3, 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)。
13C-NMR (101 MHz, CDCl3, 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), Cs2CO3(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 N2The 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, 5mL of water is added, and then the mixture is extracted by 3X 5mL of ethyl acetate, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate and 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 is 90%).
1H-NMR (400 MHz, CDCl3, 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)。
13C-NMR (101 MHz, CDCl3, 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-Bromobenzophenone (0.2 mmol)Sodium benzenesulfonate (0.4 mmol), Cs2CO3(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 N2The 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, 5mL of water was added, followed by extraction with 3 × 5mL 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%).
1H-NMR (400 MHz, CDCl3, 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)。
13C-NMR (101 MHz, CDCl3, 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 Cs2CO3(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 N2The 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, 5mL of water was added, followed by extraction with 3 × 5mL 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 60%).
1H-NMR (400 MHz, CDCl3, 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)。
13C-NMR (101 MHz, CDCl3, 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 Cs2CO3(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 N2The 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, 5mL of water was added, followed by extraction with 3 × 5mL 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 68%).
1H-NMR (400 MHz, CDCl3, 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)。
13C-NMR (101 MHz, CDCl3, 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-methyl iodobenzene to react with sodium benzene sulfinate.
4-methyl iodobenzene (0.2 mmol), sodium benzene sulfinate (0.4 mmol) and Cs2CO3(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 N2The 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, 5mL of water was added, followed by extraction with 3 × 5mL 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 74%). Cs2CO3Potassium carbonate was substituted and the remainder was unchanged to give the desired product (yield 76%).
1H-NMR (400 MHz, CDCl3, 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= 8.0Hz, 2H), 2.40 (s, 3H)。
13C-NMR (101 MHz, CDCl3, 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 Cs2CO3(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 N2The 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, 5mL of water was added, followed by extraction with 3 × 5mL 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%).
1H-NMR (400 MHz, CDCl3, 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)。
13C-NMR (101 MHz, CDCl3, 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 Cs2CO3(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 N2The 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, 5mL of water was added, followed by extraction with 3 × 5mL 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 63%).
1H-NMR (400 MHz, CDCl3, 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)。
13C-NMR (101 MHz, CDCl3, 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 Cs2CO3(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 N2The 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, 5mL of water was added, followed by extraction with 3 × 5mL 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%).
1H-NMR (400 MHz, CDCl3, 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)。
13C-NMR (101 MHz, CDCl3, 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 Cs2CO3(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 N2The 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, 5mL of water was added, followed by extraction with 3 × 5mL 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 63%).
1H-NMR (400 MHz, CDCl3, ppm): δ 8.20 – 8.13 (m, 1H), 7.92 (d,J= 7.6Hz, 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)。
13C-NMR (101 MHz, CDCl3, 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 Cs2CO3(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 N2The 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, 5mL of water was added, followed by extraction with 3 × 5mL 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 60%).
1H-NMR (400 MHz, CDCl3, 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)。
13C-NMR (101 MHz, CDCl3, 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 to react with 4-fluorobenzene sulfinic acid sodium.
4-bromobenzonitrile (0.2 mmol), 4-fluorobenzenesulfonic acid sodium salt (0.4 mmol) and Cs2CO3(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 N2The 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 was complete, 5mL of water was added followed by 3X 5mLExtracting with ethyl acetate, combining organic phases, drying the organic phases with anhydrous sodium sulfate, filtering, concentrating the filtrate by rotary evaporation, and separating by silica gel chromatography to obtain the target product (yield 89%).
1H-NMR (400 MHz, CDCl3, 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)。
13C-NMR (101 MHz, CDCl3, 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= 23.2Hz), 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 Cs2CO3(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 N2The 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, 5mL of water is added, and then the mixture is extracted by 3X 5mL of ethyl acetate, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate and filtered, and after the filtrate is concentrated by rotary evaporation, the target product is obtained by silica gel chromatography separation (yield 85%).
1H-NMR (400 MHz, CDCl3, ppm): δ 8.08 (dd,J= 8.1, 3.7 Hz, 4H), 7.82(t,J= 8.5 Hz, 4H)。
13C-NMR (101 MHz, CDCl3, 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 Cs2CO3(0.3 mmol), HEH (20 mol%) and DMSO (1 mL) plusInto a dry reaction tube with a magnetic stirrer, and then the reaction tube is filled with N2The 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, 5mL of water was added, followed by extraction with 3 × 5mL 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 62%).
1H-NMR (400 MHz, CDCl3, 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)。
13C-NMR (101 MHz, CDCl3, 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 sulfinic acid sodium to react.
4-bromobenzonitrile (0.2 mmol), sodium 4-tert-butylbenzenesulfonate (0.4 mmol), Cs2CO3(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 N2The 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, 5mL of water was added, followed by extraction with 3 × 5mL 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 63%).
1H-NMR (400 MHz, CDCl3, 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)。
13C-NMR (101 MHz, CDCl3, 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-methoxybenzenesulfinic acid sodium.
4-bromobenzonitrile (0.2 mmol)Sodium 4-methoxybenzenesulfite (0.4 mmol), Cs2CO3(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 N2The 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, 5mL of water was added, followed by extraction with 3 × 5mL 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 58%).
1H-NMR (400 MHz, CDCl3, 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)。
13C-NMR (101 MHz, CDCl3, 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 Cs2CO3(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 N2The 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, 5mL of water was added, followed by extraction with 3 × 5mL 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 78%).
1H-NMR (400 MHz, CDCl3, 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)。
13C-NMR (101 MHz, CDCl3, 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 sulfinic acid sodium to react.
4-bromobenzonitrile (0.2 mmol), sodium 3, 5-difluorobenzenesulfinate (0.4 mmol), Cs2CO3(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 N2The 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, 5mL of water was added, followed by extraction with 3 × 5mL 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%).
1H-NMR (400 MHz, CDCl3, 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)。
13C-NMR (101 MHz, CDCl3, 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 (10)

1.2,6-二甲基-1,4-二氢-3,5-吡啶二羧酸二乙酯在催化芳基卤素与芳基亚磺酸盐反应制备砜类化合物中的应用；所述芳基卤素具有如式（B）~式（E）中的任意一种所示的结构通式：1. Application of diethyl 2,6-dimethyl-1,4-dihydro-3,5-pyridinedicarboxylate in catalyzing the reaction of aryl halogen and aryl sulfinate to prepare sulfones; The base halogen has the general structural formula shown in any one of formula (B) to formula (E):
Figure DEST_PATH_IMAGE001
Figure DEST_PATH_IMAGE001
 其中：R1选自氰基、羰基、甲酸甲酯基、甲酸乙酯基、硝基、醛基、苯基、甲基或者甲氧基；X选自氯、溴或者碘；R2选自氰基或者苯甲酰基。Wherein: R 1 is selected from cyano, carbonyl, methyl formate, ethyl formate, nitro, aldehyde, phenyl, methyl or methoxy; X is selected from chlorine, bromine or iodine; R 2 is selected from cyano or benzoyl. 2.根据权利要求1所述的应用，其特征在于：所述反应在惰性气体保护下、碱存在下、溶剂中进行；所述2,6-二甲基-1,4-二氢-3,5-吡啶二羧酸二乙酯的用量为芳基卤素摩尔量的20%。2. The application according to claim 1, characterized in that: the reaction is carried out under the protection of an inert gas, in the presence of a base, and in a solvent; the 2,6-dimethyl-1,4-dihydro-3 , The amount of diethyl 5-pyridinedicarboxylate is 20% of the molar amount of aryl halogen. 3.根据权利要求2所述的应用，其特征在于：芳基卤素、芳基亚磺酸盐、碱的摩尔比为1:2:1.5。3. application according to claim 2 is characterized in that: the mol ratio of aryl halogen, aryl sulfinate, alkali is 1:2:1.5. 4.根据权利要求1所述的应用，其特征在于：所述芳基亚磺酸盐具有如式（H）~式（J）中的任意一种所示的结构通式：4. application according to claim 1 is characterized in that: described aryl sulfinate has the general structural formula shown in any one of formula (H)～formula (J):
Figure 58828DEST_PATH_IMAGE002
Figure 58828DEST_PATH_IMAGE002
 其中：R3选自氢、氟、三氟甲基、甲基、苯基、叔丁基或者甲氧基；R4选自三氟甲基或者甲基。Wherein: R 3 is selected from hydrogen, fluorine, trifluoromethyl, methyl, phenyl, tert-butyl or methoxy; R 4 is selected from trifluoromethyl or methyl. 5.根据权利要求1所述的应用，其特征在于，所述反应为在室温下，蓝色LED照射下反应24小时。5 . The application according to claim 1 , wherein the reaction is a reaction at room temperature for 24 hours under blue LED irradiation. 6 . 6.制备砜类化合物的方法，其特征在于，以2,6-二甲基-1,4-二氢-3,5-吡啶二羧酸二乙酯为催化剂，芳基卤素与芳基亚磺酸盐为原料反应制备砜类化合物；所述芳基卤素具有如式（B）~式（E）中的任意一种所示的结构通式：6. The method for preparing sulfone compounds, characterized in that, using 2,6-dimethyl-1,4-dihydro-3,5-pyridinedicarboxylate diethyl ester as a catalyst, arylhalogen and arylidene Sulfonate is used as raw material to react to prepare sulfone compounds; the aryl halogen has the general structural formula shown in any one of formula (B) to formula (E):
Figure 873332DEST_PATH_IMAGE001
Figure 873332DEST_PATH_IMAGE001
 其中：R1选自氰基、羰基、甲酸甲酯基、甲酸乙酯基、硝基、醛基、苯基、甲基或者甲氧基；X选自氯、溴或者碘；R2选自氰基或者苯甲酰基。Wherein: R 1 is selected from cyano, carbonyl, methyl formate, ethyl formate, nitro, aldehyde, phenyl, methyl or methoxy; X is selected from chlorine, bromine or iodine; R 2 is selected from cyano or benzoyl. 7.根据权利要求6所述制备砜类化合物的方法，其特征在于：所述反应在惰性气体保护下、碱存在下、溶剂中进行；所述2,6-二甲基-1,4-二氢-3,5-吡啶二羧酸二乙酯的用量为芳基卤素摩尔量的20%。7 . The method for preparing sulfone compounds according to claim 6 , wherein the reaction is carried out under the protection of an inert gas, in the presence of a base, and in a solvent; the 2,6-dimethyl-1,4- The amount of diethyl dihydro-3,5-pyridinedicarboxylate used is 20% of the molar amount of the aryl halogen. 8.根据权利要求7所述制备砜类化合物的方法，其特征在于：所述芳基卤素、芳基亚磺酸盐、碱的摩尔比为1:2:1.5。8 . The method for preparing sulfone compounds according to claim 7 , wherein the molar ratio of the aryl halogen, the aryl sulfinate and the base is 1:2:1.5. 9 . 9.根据权利要求7所述制备砜类化合物的方法，其特征在于：所述芳基亚磺酸盐具有如式（H）~式（J）中的任意一种所示的结构通式：9. The method for preparing sulfone compounds according to claim 7, wherein the aryl sulfinate has the general structural formula shown in any one of formula (H)～formula (J):
Figure 806653DEST_PATH_IMAGE002
Figure 806653DEST_PATH_IMAGE002
 其中：R3选自氢、氟、三氟甲基、甲基、苯基、叔丁基或者甲氧基；R4选自三氟甲基或者甲基。Wherein: R 3 is selected from hydrogen, fluorine, trifluoromethyl, methyl, phenyl, tert-butyl or methoxy; R 4 is selected from trifluoromethyl or methyl. 10.根据权利要求7所述制备砜类化合物的方法制备的砜类化合物。10. The sulfone compound prepared by the method for preparing the sulfone compound according to claim 7.
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