CN113185434A - Synthetic method of diaryl sulfone compound - Google Patents
Synthetic method of diaryl sulfone compound Download PDFInfo
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- CN113185434A CN113185434A CN202110401585.8A CN202110401585A CN113185434A CN 113185434 A CN113185434 A CN 113185434A CN 202110401585 A CN202110401585 A CN 202110401585A CN 113185434 A CN113185434 A CN 113185434A
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Abstract
The invention discloses a method for catalyzing aryltriazenes and DABCO (SO) by using iron-containing Lewis acidic ionic liquid2)2And a green synthesis method for synthesizing diaryl sulfone compounds by a three-component one-pot method of beta-naphthol. At the temperature of 90 ℃, iron-containing Lewis acidic ionic liquid is used as a catalyst, aryltriazene is used as an aryl source, and DABCO (SO) is used2)2As SO2And (3) a source, and the sulphonation reaction of the C1 position of the beta-naphthol is realized. The advantages of the invention include: the reaction is green, the operation is simple, and no additive is needed; the raw materials are cheap and easily available, the source is wide, the preparation is simple, and the structure is stable; the used catalyst is iron-containing ionic liquid which is cheap and easy to obtain, and has the advantages of simple preparation, low price, stable structure, small pollution, environmental protection and the like.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a diaryl sulfone derivative obtained by using aryl triazene as an aryl source to realize a sulphonation reaction at a C1 site of beta-naphthol under the catalysis of an iron-containing Lewis acidic ionic liquid.
Background
Aryl sulfones are important chemical raw materials and chemical products, and are very common in research fields of medicine, pesticide, polymer science, material science and the like due to the particularity of structural fragments thereof (Trost, B.M.; Shen, H.C.; Surivet, J.P.J.am.chem.Soc.2004,126, 12565; Adams, C.M.; Ghosh, I.; shi, Y.Org.Le2004, 6,4723; Kochi, T.; Noda, S.; Yoshimura, K.; Nozaki, K.J.am.chem.Soc.2007,129, 8948; Wang, M.; Chen S.H.; Jiang, X.F.Org.Lett.2017,19,4916.Moss, Diurdao.C.; K.K.N.K.; Bon.H.; Ji J.H.; Jiang, X.F.H.; X.H.; X.M. K.2015 J.S.S.H.; U.S.S.S.S.S.; U.S.W.W.W.W.W.W.W.W.W.W.W.W.W.J.S. K. A. K. H.; U.7, U.H. K. H. K. H. K. H. K. J. K. H. K.. It is widely used in the fields of pharmaceuticals, organic synthetic, polymeric compounds (Popoff, I.C.; Engle, A.R.; Whitaker, R.L.; Singhal, G.H.J.Med.Chem.1971,14,1166; Spanhoff, A.; Heinke, R.; Bauer, I.; Trojer, P.; Metzger, E.; Gust, R.; Schuel, R.; Brosch, G.; Sippl, W.; Jung., M.J.Chem.2007, 50,2319; Guo, M.Li, X.; Li, L.; Yu Y.; Song, Y.; Liu, B.; Jiang, Z.J.Sci.2011, 380, 171; H.; Fang, X.; Yang, Y.; Liu B.; Juang, Z.J.541, Sch U.2011, U.821, B.; Jian Ji J.541, U.7, U.103; Wilford Sulpha J.S.P., Sulph J.540; Sulph H.A.7, Sulph, Sulph K.; Sulph and Sulph, Sulph and K.7, Sulph, Sulph and Sulph, Sulph et, Sulph and Sulph A.7, Sulph et, Sulph A.7, Sulph et A.7, Sulph et, Sulph and Sulph A.7, Sulph et, Sulph K. (Sulph A.7, Sulph et, Sulph and Sulph, Sulph, Sulph and Sulph et, Sulph A.7, Sulph et, Sulph et, Sulph and Sulph et, Sulph et, Sulph K, Sulph et, Sulph et, Sulph et, Sulph K, Sulph and Sulph et, and Sulph et, and Sulph et, Sulph K, and Sulph et, Sulph K, and Sulph et, Sulph et al, Sulph et, and Sulph et, Sulph et al, and Sulph et al, and Sulph et, and Sulph et, and Sulph et al, and Sulph et, and Sulph et, and Sulph, expert opin. pharmacother.2002,3,1313; s.s. simpkins, Sulfones in Organic Synthesis, Pergamon Press, Oxford, 1993; g) p.prasit, z.wang, c.brideau, c.c.chan, s.charleson, w.cromlish, d.ethier, j.f.evans, a.w.f. -Hutchinson, j.y.gaulthier, r.gordon, j.guay, m.gresser, s.kargman, b.kennedy, y.leblanc, s.l iger, j.mancini, g.p.o' Neill, m.ouellet, m.d.perceival, h.percier, d.rieau, i.rodour, p.tagari, m.th é rien, p.vickers, e.wong, l.j.xu, r.n.yung, r.bou, r.bouganic, s.boudouke, p.tagari, r.t, r.r.t, r.r.r.t, boudouke, r.t, r.t.t.t, r.t. t, r.t. t. r.t, r.t. r, r.t. r. r.t. r.r.t. r, r.t. r.r.r.t. r.r.t. r.r.r.r.r.t. r.t. r.r.r.t. r.r.r.r, r. r.r, r.r.t. r.r.r, r, r.r.r.r.r.r.r, r.r.r, r.r.r.r.r.r.r, r.r.r.r.r.r.r.r.r, r, r.r.r, r.r.r.r.t. r.r, r.r.r.r.r.r.r, r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r, r.r.r.r.r.r.r.r.r, r, r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r, r.r.r.r, r, r.r.r.r, r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r, r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r, r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r.r, r.r.r.r.r.r.r, r.r.r; toth, a.; cassan, c.; czuriga, d.; tomb, p.p.; papp, z.; lacampagne, a.; cazorla, o.cardiovasc.res.2011,91,412; fowler, j.s.; logan, j.neuropsychopharmacology 2010,35, 623; waters, m.f.; rees, r.j.; mc Dougall, a.c.; weddell, a.g.t.lepr.rev.1974,45,288.), 1996, the arico subject group reported that diaryl sulfones inhibit HIV-1 reverse transcriptase (arico, m.; silvestri, r.; massa, s.; loi, a.g.; coriias, s.; piras, g.; la Colla, p.j.med.chem.1996,39,522.); the Dubac group and Rao group reported that diphenyl sulfone could be used as an intermediate in the synthesis of 4, 4' -diaminodiphenyl sulfone (IV-1), which is a potent drug for the treatment of leprosy (R pi chet, S.; Le Roux, C.; Hernandez, P.; Dubac, J.; Desmurs, J.R.J.Org.Chem.1999,64,6479; Yang, Y.; Chen, Z.; Rao, Y.Chem.Commun.2014,50,15037.); sulfadiazine (IV-2) and other sulfonamides are widely used clinically against bacteria, fungi (Quesnel, L.B.; Al-Najjar, A.R.; Buddhavudhikrai, P.J. appl.Bacteriol.1978,45,397.); celecoxib (IV-3) is an anti-inflammatory agent useful in alleviating symptoms of osteoarthritis and rheumatoid arthritis (Penning, t.d.; Talley, j.j.; Bertenshaw, s.r.; Carter, j.s.; Collins, p.w.; docker, s.; graneo, m.j.; Lee, l.f., Malecha, j.w.; Miyashiro, j.w.; Rogers, r.s.; Rogier, d.j.; Yu s.s.; Anderson, g.d.; Burton, e.g., Cogburn, j.n.; Gregory, s.a., Koboldt, c.m.; Perkins, w.e.; seert, k.; neen, j.n., zhaky.1997, ishuh.; c.s.s.; seik j.; et h.s.s.s.s.; meclorthiazine (IV-4) is a diuretic drug used clinically for edema, hypertension of various stages and diabetes insipidus, and is often used in combination with antihypertensive drug deserpidine for treating hypertension Colas, B.; slama, m.; masson, h.; colas, j.l.; collin, T.; arnould, m.l.; hary, l.; safar, m.; andrejak, m.fundam.clin.pharmacol.2000,14,363.). Because of the important role of aryl sulfone in organic synthesis and pharmaceutical chemistry, the synthesis of aryl sulfone compounds is widely researched.
Disclosure of Invention
The invention overcomes the defects of aryl triazene activation (such as needing equivalent acid as a promoter), and realizes the sulphonation reaction of the C1 site of beta-naphthol in a green and high-efficiency way under the condition of only needing catalytic amount of iron-containing ionic liquid, without the promoter and without the protection of inert gas.
The invention uses the iron-containing ionic liquid which is environment-friendly, cheap and easily available as the catalyst, and uses the triazenes which are simple to prepare and have wide sources as the raw material to realize the three-component one-pot sulphonation reaction.
The 1-aryl sulfonyl-2-naphthol compound (IV) in the following reaction formula is prepared by the method;
wherein the reaction process is shown as the following reaction formula;
wherein
R1A series of substituents at different positions of ortho-position, meta-position, para-position and the like of a benzene ring;
R2the method comprises the following steps:
in the invention, R2Not limited to the above groups.
As shown in the reaction formula, the invention uses iron-containing ionic liquid which is cheap and easy to prepare as a catalyst, and takes beta-naphthol (I), triazene compound (II) and DABSO (SO) without promoter2)2(III) as a raw material, and the 1-arylsulfonyl-2-naphthol compound (IV) is obtained by realizing a three-component one-pot reaction at a certain temperature
In the invention, the iron-containing ionic liquid used in the reaction is
Preferably, the iron-containing ionic liquid is IL 4.
In the invention, the molar amount of the iron-containing ionic liquid used in the reaction is 5-100% of that of the beta-naphthol. Preferably, the molar amount of the iron-containing ionic liquid used is 20% of that of the beta-naphthol.
In the present invention, the reaction temperature in the reaction is 40 to 100 ℃, preferably, the reaction temperature is 90 ℃.
In the present invention, in the reaction, beta-naphthol, aryltriazene, DABCO (SO)2)2The molar ratio of the used amount is 1:1:0.8-1:1.5:1.2, preferably beta-naphthol, aryltriazene, DABCO (SO)2)2The molar ratio of the dosage is 1:1.5:1.2 or 1:1.5:0.8, more preferably beta-naphthol, aryl triazene and DABCO (SO)2)2The molar ratio of the amounts used was 1:1.5: 1.2.
In the invention, the reaction solvent is acetonitrile and 1, 2-dichloroethane. Preferably, the reaction solvent is acetonitrile.
In the invention, the reaction time is 12-16 h. Preferably, the reaction time is 14 h.
The synthesis reaction of the invention comprises the following steps:
synthesis of 1-arylsulfonyl-2-naphthol Compound (IV):
adding iron-containing ionic liquid IL 4(20 mol%), beta-naphthol (I) (X mmol), aryltriazene (II) (Ymmol) and DABCO (SO) into the sealed tube in sequence2)2(III) (Z mmol) and solvent CH3CN (U mL) and stirring for 14h at the temperature of 90 ℃ to obtain the reaction product 1-arylsulfonyl-2-naphthol (IV).
The invention overcomes the defects of aryl triazene activation, such as needing equivalent acid as an accelerant and realizing the C-H bond activation sulphonation reaction of the 1-position of beta-naphthol in a green and high-efficiency manner under the condition of only needing catalytic amount of ionic liquid. All the raw materials used in the invention are industrial commodities, and the raw materials are cheap, easily available, wide in source, simple and easily available and wide in source; the catalyst used in the invention is iron-containing ionic liquid which is cheap and easy to obtain, and has the advantages of simple preparation, low price, stable structure, little pollution and environmental protection; the reaction is green, the operation is simple, and no additive is needed.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of 1- (4-methyl) benzenesulfonyl-2-naphthol, a product of example 1
FIG. 2 is a nuclear magnetic hydrogen spectrum of 1-benzenesulfonyl-2-naphthol, the product of example 35
FIG. 3 is a nuclear magnetic hydrogen spectrum of 1- (2-methyl) benzenesulfonyl-2-naphthol, a product of example 36
FIG. 4 is a nuclear magnetic hydrogen spectrum of 1- (3-methyl) benzenesulfonyl-2-naphthol, a product of example 37
FIG. 5 is a nuclear magnetic hydrogen spectrum of 1- (2, 6-dimethyl) benzenesulfonyl-2-naphthol, a product of example 38
FIG. 6 is a nuclear magnetic hydrogen spectrum of 1- (4-ethyl) benzenesulfonyl-2-naphthol, a product of example 39
FIG. 7 is a nuclear magnetic hydrogen spectrum of 1- (4-tert-butyl) benzenesulfonyl-2-naphthol, a product obtained in example 40
FIG. 8 is a nuclear magnetic hydrogen spectrum of 1- (4-methoxy) benzenesulfonyl-2-naphthol, a product of example 41
FIG. 9 is a nuclear magnetic hydrogen spectrum of 1- (3-methylthio) benzenesulfonyl-2-naphthol, a product of example 42
FIG. 10 is a nuclear magnetic hydrogen spectrum of 4- (4-methyl) benzenesulfonylphenol which is the product of example 43
Detailed Description
The present invention will be described in further detail with reference to the following specific examples, but the present invention is not limited to the following examples. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, and the scope of the appended claims is intended to be protected. The procedures, conditions, reagents, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited. The data given in the examples below include specific operating and reaction conditions and products. The purity of the product was identified by nuclear magnetism.
Example 1: synthesis of 1- (4-methyl) benzenesulfonyl-2-naphthol
The dry clean sealed tube was charged with the iron-containing ionic liquid IL 4(20 mol%, 0.04mmol,17.9mg relative to 1a), followed by the addition of the reaction substrates β -naphthol (1a) (0.2mmol,28.8mg), (4-methyl) phenyltriazene (2a) (0.3mmol,56.7mg) and DABCO (SO)2)2(3a) (0.24mmol,57.6mg), followed by addition of solvent CH3CN (2mL), the tube opening of the tube is sealed and the reaction is stirred for 14h at the temperature of 90 ℃. After completion of the reaction, 5mL of water was added to the reaction system to quench the reaction, and the aqueous mixture was extracted with ethyl acetate (3X 5mL, 3 times in total, 5mL each). After the extraction, the organic phase was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure, and purified by column chromatography (eluent: petroleum ether/ethyl acetate 50:1-30:1, v/v, (here, 40:1)) to give a yellow solid (51.8mg, 87%). Detecting the obtained target product by adopting an infrared and nuclear magnetic resonance spectrometer; the nuclear magnetic parameters of the obtained product are1H NMR(400MHz,CDCl3) δ 11.14(s,1H),8.35(d, J ═ 8.7Hz,1H),7.92(d, J ═ 9.0Hz,1H),7.84(d, J ═ 8.4Hz,2H),7.71(d, J ═ 8.7Hz,1H),7.49-7.43(m,1H),7.30-7.36(m,1H),7.28(s,1H),7.26(s,1H),7.18(d, J ═ 9.0Hz,1H),2.36(s,3H).
Example 2
The dry clean sealed tube was charged with IL 4(20 mol%, 0.04mmol,17.9mg relative to 1a) as an iron-containing ionic liquid, followed by the addition of the reaction substrates β -naphthol (1a) (0.2mmol,28.8mg), (4-methyl) phenyltriazene (2a) (0.3mmol,56.7mg) and Na2S2O3.5H2O (3b) (0.2mmol,49.6mg), followed by addition of solvent CH3CN (2mL), the tube opening of the tube is sealed and the reaction is stirred for 14h at the temperature of 90 ℃. After the reaction is finished, the obtained target product is determined by adopting an infrared and nuclear magnetic resonance instrument, and the target product is found to be obtained only in trace yield, which indicates that Na is used2S2O3.5H2O as SO2When it is sourced, the yield of the target product is low.
Example 3
The dry clean sealed tube was charged with the iron-containing ionic liquid IL 4(20 mol%, 0.04mmol,17.9mg relative to 1a), followed by the addition of the reaction substrates β -naphthol (1a) (0.2mmol,28.8mg), (4-methyl) phenyltriazene (2a) (0.3mmol,56.7mg) and Na2S2O4(3c) (0.2mmol,34.8mg), followed by addition of solvent CH3CN (2mL), the tube opening of the tube is sealed and the reaction is stirred for 14h at the temperature of 90 ℃. After the reaction was completed, the target product was confirmed by infrared and nuclear magnetic resonance spectroscopy, and it was found that the target product 4a was only 7.1mg, the yield was 12%, indicating that Na was used2S2O4As SO2The yield of the target product is low when it is sourced.
Example 4
The dry clean sealed tube was charged with IL 4(20 mol%, 0.04mmol,17.9mg relative to 1a) as an iron-containing ionic liquid, followed by the addition of the reaction substrates β -naphthol (1a) (0.2mmol,28.8mg), (4-methyl) phenyltriazene (2a) (0.3mmol,56.7mg) and Na2S2O5(3d) (0.2mmol,38.0mg), followed by addition of solvent CH3CN (2mL), the tube opening of the tube is sealed and the reaction is stirred for 14h at the temperature of 90 ℃. After the reaction was completed, the target product obtained was confirmed by infrared and nuclear magnetic resonance spectroscopy, and it was found that the target product 4a was obtained in an amount of only 16.1mg in a yield of 27%, indicating that Na was used2S2O4As SO2When the source is used, the yield of the target product is low.
Example 5
The dry clean sealed tube was charged with IL 4(20 mol%, 0.04mmol,17.9mg relative to 1a) as an iron-containing ionic liquid, followed by the addition of the reaction substrates β -naphthol (1a) (0.2mmol,28.8mg), (4-methyl) phenyltriazene (2a) (0.3mmol,56.7mg) and Na2SO3(3e) (0.2mmol,25.2mg), followed by addition of solvent CH3CN (2mL), the tube opening of the tube is sealed and the reaction is stirred for 14h at the temperature of 90 ℃. After the reaction is completed, the obtained target product is determined by adopting an infrared and nuclear magnetic resonance instrument, and the target product is found to be obtained only in trace yield, which indicates that Na is used2S2O4As SO2When the source is used, the yield of the target product is low.
Example 6
The dry clean sealed tube was charged with the iron-containing ionic liquid IL 4(20 mol%, 0.04mmol,17.9mg relative to 1a), followed by the addition of the reaction substrates β -naphthol (1a) (0.2mmol,28.8mg), (4-methyl) phenyltriazene (2a) (0.3mmol,56.7mg) and K2S2O8(3f) (0.2mmol,54.0mg), followed by addition of solvent CH3CN (2mL), the tube opening of the tube is sealed and the reaction is stirred for 14h at the temperature of 90 ℃. After the reaction is finished, the obtained target product is determined by adopting an infrared and nuclear magnetic resonance instrument, and the target product is found to be obtained only in trace yield, which indicates that K is used2S2O8As SO2When the source is used, the yield of the target product is low.
Example 7
The reaction procedure and operation conditions were the same as in example 1, except that dimethyl sulfoxide was added instead of acetonitrile in the reaction, as in example 1. The reaction was stopped, the same post-treatment as above, and the target product obtained was determined by infrared and nuclear magnetic resonance spectroscopy to give target product 4a (5.2mg, 9% yield), indicating that the yield of the target product was low when dimethyl sulfoxide was the solvent.
Example 8
The reaction procedure and operation conditions were the same as in example 1, except that dichloroethane was added instead of acetonitrile in the reaction, as in example 1. The reaction was stopped, the same post-treatment as above, and the target product obtained was determined by infrared and nuclear magnetic resonance spectroscopy to obtain target product 4a (27.0mg, 45% yield), indicating that the better target product could be obtained when dichloroethane was the solvent.
Example 9
The reaction procedure and operation conditions were the same as in example 1, except that ethyl acetate was added in place of acetonitrile in the reaction, as in example 1. Stopping reaction, carrying out the same post-treatment as above, and detecting by an infrared and nuclear magnetic resonance spectrometer to obtain no target product 4 a. Indicating that the reaction cannot take place using ethyl acetate as solvent.
Example 10
The reaction procedure and operation conditions were the same as in example 1, except that ethanol was added instead of acetonitrile in the reaction, as in example 1. Stopping reaction, carrying out the same post-treatment as above, and determining the obtained target product by using an infrared and nuclear magnetic resonance spectrometer to obtain only trace target product 4 a. The ethanol is used as the solvent, so that the yield of the target product is low.
Example 11
The reaction procedure and operation conditions were the same as in example 1, except that 1, 4-dioxane was added instead of acetonitrile in the reaction, as in example 1. The reaction was stopped, and after the same post-treatment as above, no target product 4a was obtained by infrared and nuclear magnetic resonance spectroscopy, indicating that the reaction could not occur using 1, 4-dioxane as the solvent.
Example 12
The reaction procedure and operation conditions were the same as in example 1, except that the reaction was carried out at room temperature, as in example 1. The reaction was stopped, the same post-treatment as above, and the target product obtained was determined by infrared and nuclear magnetic resonance spectroscopy to give target product 4a (5.8mg, 10% yield), indicating that the reaction was at room temperature with a lower yield of the target product.
Example 13
The reaction procedure and operation conditions were the same as in example 1, except that the reaction was carried out at 40 ℃. The reaction was stopped, the same post-treatment as above, and the target product obtained was confirmed by infrared and nuclear magnetic resonance spectroscopy to give target product 4a (16.2mg, 27% yield), indicating that the reaction gave the target product at 40 ℃ with a better yield.
Example 14
The reaction procedure and operation conditions were the same as in example 1, except that the reaction was carried out at 60 ℃. The reaction was stopped, the same post-treatment as above, and the target product obtained was determined by infrared and nuclear magnetic resonance spectroscopy to obtain the target product 4a (19.3mg, 32% yield), indicating that the reaction gave the target product at a better yield at 60 ℃.
Example 15
The reaction procedure and operation conditions were the same as in example 1, except that the reaction was carried out at 70 ℃. The reaction was stopped, the same post-treatment as above, and the target product obtained was confirmed by infrared and nuclear magnetic resonance spectroscopy to give the target product 4a (34.6mg, 58% yield), indicating that the reaction gave the target product at a better yield at 70 ℃.
Example 16
The reaction procedure and operation conditions were the same as in example 1, except that the reaction was carried out at 80 ℃. The reaction was stopped, and after the same procedure as above, the target product obtained was determined by infrared and nuclear magnetic resonance spectroscopy and processed to give the target product 4a (35.7mg, 60% yield), indicating that the reaction gave the target product at 80 ℃ with a better yield.
Example 17
The reaction procedure and operation conditions were the same as in example 1, except that the reaction was carried out at 100 ℃. The reaction was stopped, the same post-treatment as above, and the target product obtained was determined by infrared and nuclear magnetic resonance spectroscopy to obtain the target product 4a (35.9mg, 60% yield), indicating that the reaction gave the target product at a better yield at 100 ℃.
Example 18
The reaction procedure and operating conditions were the same as in example 1, except that the ratio of 1a, 2a, 3a in the reaction was 1:1:0.8, as in example 1. The reaction was stopped, the same post-treatment as above was carried out, and the target product obtained was confirmed by infrared and nuclear magnetic resonance spectroscopy to obtain the target product 4a (40.6mg, yield 68%), indicating that the target product could be obtained with a better yield under the conditions that the ratio of 1a, 2a, 3a in the reaction was 1:1: 0.8.
Example 19
The reaction procedure and operating conditions were the same as in example 1, except that the ratio of 1a, 2a, 3a in the reaction was 1:1.5:0.8, as in example 1. The reaction was stopped, the same post-treatment as above, and the target product obtained was determined by infrared and nuclear magnetic resonance spectroscopy to obtain target product 4a (47.2mg, 79% yield), indicating that the preferred target product could be obtained at a 1:1.5:0.8 ratio of 1a, 2a, 3a in the reaction.
Example 20
The reaction procedure and operating conditions were the same as in example 1, except that the ratio of 1a, 2a, 3a in the reaction was 1:1:1, as in example 1. The reaction was stopped, the same post-treatment as above was carried out, and the target product obtained was confirmed by infrared and nuclear magnetic resonance spectroscopy to obtain the target product 4a (32.2mg, 54% yield), indicating that the target product could be obtained with a better yield under the condition that the ratio of 1a, 2a, 3a in the reaction was 1:1:1.
Example 21
The reaction procedure and operating conditions were the same as in example 1, except that the ratio of 1a, 2a, 3a in the reaction was 1:1: 1.2. The reaction was stopped, the same post-treatment as above was carried out, and the obtained target product was determined by infrared and nuclear magnetic resonance spectroscopy to obtain target product 4a (40.3mg, yield 67%), indicating that the target product could be obtained with a better yield under the conditions that the ratio of 1a, 2a, 3a in the reaction was 1:1: 1.2.
Example 22
The reaction procedure and operation conditions were the same as in example 1, except that the reaction time was 12 hours, as compared with example 1. The reaction was stopped, the same post-treatment as above, and the target product obtained was determined by infrared and nuclear magnetic resonance spectroscopy to give target product 4a (48.8mg, 82% yield), indicating that the preferred target product could be obtained under reaction conditions of 12 h.
Example 23
The reaction procedure and operation conditions were the same as in example 1, except that the reaction was carried out for 16 hours, as in example 1. The reaction was stopped, the same post-treatment as above, and the target product obtained was determined by infrared and nuclear magnetic resonance spectroscopy to give target product 4a (49.2mg, 82% yield), indicating that the preferred target product could be obtained under the reaction condition of 16 h.
Example 24
The reaction procedure and operation conditions were the same as in example 1, except that the amino moiety in the aryltriazenes was
Stopping reaction, performing the same post-treatment as above, and determining the obtained target product with infrared and nuclear magnetic resonance spectrometer to obtain target product 4a (48.3mg, yield 81%), which indicates that the amino part in the aryltriazene is
Under the condition, a better target product can be obtained.
Example 25
The reaction procedure and operation conditions were the same as in example 1, except that the amino moiety in the aryltriazenes was
Stopping reaction, performing the same post-treatment as above, and determining the obtained target product with infrared and nuclear magnetic resonance spectrometer to obtain target product 4a (46.5mg, yield 78%), which indicates that the amino part in the aryltriazene is
Under the condition, a better target product can be obtained.
Example 26
The reaction procedure and operation conditions were the same as in example 1, except that the amino moiety in the aryltriazenes was
Stopping reaction, performing the same post-treatment as above, and determining the obtained target product with infrared and nuclear magnetic resonance spectrometer to obtain target product 4a (51.5mg, yield 87%), which indicates that the amino part in the aryltriazene is
Under the condition, a better target product can be obtained.
Example 27
The reaction procedure and operation conditions were the same as in example 1, except that the amino moiety in the aryltriazenes was
Stopping reaction, performing the same post-treatment as above, and determining the obtained target product with infrared and nuclear magnetic resonance spectrometer to obtain target product 4a (33.9mg, yield 57%), which indicates that the amino part in the aryltriazene is
Under the condition, the target product can be obtained with a better yield.
Example 28
The reaction procedure and operation conditions were the same as in example 1, except that the amino moiety in the aryltriazenes was
Stopping reaction, performing the same post-treatment as above, and determining the obtained target product with infrared and nuclear magnetic resonance spectrometer to obtain target product 4a (43.5mg, 73% yield), which indicates that the amino part in the aryltriazene is
Under the condition, a better target product can be obtained.
Example 29
The reaction procedure and operation conditions were the same as in example 1, except that the amino moiety in the aryltriazenes was
Stopping reaction, performing the same post-treatment as above, and determining the obtained target product with infrared and nuclear magnetic resonance spectrometer to obtain target product 4a (33.9mg, yield 57%), which indicates that the amino part in the aryltriazene is
Under the condition, the target product can be obtained with a better yield.
Example 30
The reaction procedure and operation conditions were the same as in example 1, except that the amino moiety in the aryltriazenes was
Stopping reaction, performing the same post-treatment as above, and determining the obtained target product with infrared and nuclear magnetic resonance spectrometer to obtain target product 4a (40.5mg, yield 68%), which indicates that the amino part in the aryltriazene is
Under the condition, the target product can be obtained with a better yield.
Example 31
The reaction procedure and operation conditions were the same as in example 1, except that the amino moiety in the aryltriazenes was
Stopping reaction, performing the same post-treatment as above, and determining the obtained target product with infrared and nuclear magnetic resonance spectrometer to obtain target product 4a (40.5mg, yield 68%), which indicates that the amino part in the aryltriazene is
Under the condition, the target product can be obtained with a better yield.
Example 32
The reaction procedure and operation conditions were the same as in example 1, except that aryltris (phenyl) is used as the reaction product in example 1The amino moiety in the nitrene is
Stopping reaction, performing the same post-treatment as above, and determining the obtained target product with infrared and nuclear magnetic resonance spectrometer to obtain target product 4a (42.3mg, yield 71%), which indicates that the amino part in the aryltriazene is
Under the condition, the target product can be obtained with better yield.
Example 33
The reaction procedure and operation conditions were the same as in example 1, except that the amino moiety in the aryltriazenes was
Stopping reaction, performing the same post-treatment as above, and determining the obtained target product with infrared and nuclear magnetic resonance spectrometer to obtain target product 4a (48.9mg, yield 82%), which indicates that the amino part in the aryltriazene is
Under the condition, a better target product can be obtained.
Example 34
The reaction procedure and operation conditions were the same as in example 1, except that the amino moiety in the aryltriazenes was
Stopping reaction, performing the same post-treatment as above, and determining the obtained target product with infrared and nuclear magnetic resonance spectrometer to obtain target product 4a (48.3mg, yield 81%), which indicates that the amino part in the aryltriazene is
Under the condition, a better target product can be obtained.
Example 35: synthesis reaction of 1-benzenesulfonyl-2-naphthol
The dry clean sealed tube was charged with iron-containing ionic liquid IL 4(20 mol% relative to 1a, 0.04mmol,17.9mg), followed by the addition of the reaction substrates β -naphthol (1a) (0.2mmol,28.8mg), phenyltriazene (2b) (0.3mmol,52.2mg) and DABCO (SO)2)2(3a) (0.24mmol,57.6mg), followed by addition of solvent CH3CN (2mL), the tube opening of the tube is sealed and the reaction is stirred for 14h at the temperature of 90 ℃. After completion of the reaction, 5mL of water was added to the reaction system to quench the reaction, and the aqueous mixture was extracted with ethyl acetate (3X 5mL, 3 times in total, 5mL each). After the extraction, the organic phase was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure, and isolated and purified by column chromatography (eluent: petroleum ether/ethyl acetate 50:1-30:1, v/v, (here 40:1)) to give an orange solid (48.3mg, 90%). Determining the obtained target product by adopting an infrared and nuclear magnetic resonance spectrometer; the nuclear magnetic parameters of the obtained product are1H NMR(400MHz,CDCl3)δ11.12(s,1H),8.33(d,J＝8.7Hz,1H),7.96(s,1H),7.94(s,1H),7.91(d,J＝9.0Hz,1H),7.72(dd,J＝17.8,8.5Hz,2H),7.49-7.54(m,1H),7.47(d,J＝7.9Hz,2H),7.31(d,J＝7.3Hz,1H),7.18(d,J＝9.1Hz,1H).
Example 36: synthesis reaction of 1- (2-methyl) benzenesulfonyl-2-naphthol
The dry clean sealed tube was charged with the iron-containing ionic liquid IL 4(20 mol%, 0.04mmol,17.9mg relative to 1a), followed by the addition of the reaction substrates β -naphthol (1a) (0.2mmol,28.8mg), (2-methyl) phenyltriazene (2c) (0.3mmol,56.7mg) and DABCO (SO)2)2(3a) (0.24mmol,57.6mg), followed by addition of solvent CH3CN (2mL), the tube opening of the tube is sealed and the reaction is stirred for 14h at the temperature of 90 ℃. After completion of the reaction, 5mL of water was added to the reaction system to quench the reaction, and the aqueous mixture was extracted with ethyl acetate (3X 5mL, 3 times in total, 5mL each).After the extraction, the organic phase was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure, and isolated and purified by column chromatography (eluent: petroleum ether/ethyl acetate 50:1-30:1, v/v, (here 40:1)) to give an orange solid (42.3mg, 71%). Determining the obtained target product by adopting an infrared and nuclear magnetic resonance spectrometer; the nuclear magnetic parameters of the obtained product are1H NMR(400MHz,CDCl3)δ11.15(s,1H),8.32(dd,J＝7.5,1.9Hz,1H),8.11(d,J＝8.7Hz,1H),7.95(d,J＝9.0Hz,1H),7.74-7.70(m,1H),7.47-7.42(m,2H),7.42-7.38(m,1H),7.34-7.30(m,1H),7.20(s,1H),7.18(s,1H),2.37(s,3H).
Example 37: synthesis reaction of 1- (3-methyl) benzenesulfonyl-2-naphthol
The dry clean lock tube was charged with the iron-containing ionic liquid IL 4(20 mol%, 0.04mmol,17.9mg relative to 1a), followed by the addition of the reaction substrates β -naphthol (1a) (0.2mmol,28.8mg), (3-methyl) phenyltriazene (2d) (0.3mmol,56.7mg) and DABCO (SO)2)2(3a) (0.24mmol,57.6mg), followed by addition of solvent CH3CN (2mL), the tube opening of the tube is sealed and the reaction is stirred for 14h at the temperature of 90 ℃. After completion of the reaction, 5mL of water was added to the reaction system to quench the reaction, and the aqueous mixture was extracted with ethyl acetate (3X 5mL, 3 times in total, 5mL each). After the extraction, the organic phase was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure, and isolated and purified by column chromatography (eluent: petroleum ether/ethyl acetate 50:1-30:1, v/v, (here 40:1)) to give an orange solid (44.7mg, 75%). Determining the obtained target product by adopting an infrared and nuclear magnetic resonance spectrometer; the nuclear magnetic parameters of the obtained product are1H NMR(400MHz,CDCl3)δ11.14(s,1H),8.34(dd,J＝8.7,0.7Hz,1H),7.94(d,J＝9.0Hz,1H),7.70-7.79(m,3H),7.43-7.49(m,1H),7.40-7.31(m,3H),7.19(d,J＝9.0Hz,1H),2.38(s,3H).
Example 38: synthesis reaction of 1- (2, 6-dimethyl) benzenesulfonyl-2-naphthol
The dry clean sealed tube was charged with the iron-containing ionic liquid IL 4(20 mol%, 0.04mmol,17.9mg relative to 1a), followed by the addition of the reaction substrates β -naphthol (1a) (0.2mmol,28.8mg), (2, 6-dimethyl) phenyltriazene (2e) (0.3mmol,60.7mg) and DABCO (SO)2)2(3a) (0.24mmol,57.6mg), followed by addition of solvent CH3CN (2mL), the tube opening of the tube is sealed and the reaction is stirred for 14h at the temperature of 90 ℃. After completion of the reaction, 5mL of water was added to the reaction system to quench the reaction, and the aqueous mixture was extracted with ethyl acetate (3X 5mL, 3 times in total, 5mL each). After the extraction, the organic phase was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure, and purified by column chromatography (eluent: petroleum ether/ethyl acetate 50:1-30:1, v/v, (here, 40:1)) to give an orange solid (23.1mg, 37%). Determining the obtained target product by adopting an infrared and nuclear magnetic resonance spectrometer; the nuclear magnetic parameters of the obtained product are1H NMR(400MHz,CDCl3)δ11.10(s,1H),7.92(d,J＝9.1Hz,1H),7.76-7.70(m,2H),7.34-7.26(m,3H),7.15(d,J＝9.1Hz,1H),7.11(d,J＝7.7Hz,2H),2.61(s,6H).
Example 39: synthesis reaction of 1- (4-ethyl) benzenesulfonyl-2-naphthol
The dry clean lock tube was charged with the iron-containing ionic liquid IL 4(20 mol%, 0.04mmol,17.9mg relative to 1a), followed by the addition of the reaction substrates β -naphthol (1a) (0.2mmol,28.8mg), (4-ethyl) phenyltriazene (2f) (0.3mmol,60.7mg) and DABCO (SO)2)2(3a) (0.24mmol,57.6mg), followed by addition of solvent CH3CN (2mL), the tube opening of the tube is sealed and the reaction is stirred for 14h at the temperature of 90 ℃. After completion of the reaction, 5mL of water was added to the reaction system to quench the reaction, and the aqueous mixture was extracted with ethyl acetate (3X 5mL, 3 times in total, 5mL each). After extraction the organic phase is dried over anhydrous magnesium sulphate, filtered and concentrated under reduced pressure and fractionated by column chromatography (eluent: petroleum ether/ethyl acetate 50:1-30:1, v/v (here 40:1))Purification afforded an orange solid (47.5mg, 76%). Determining the obtained target product by adopting an infrared and nuclear magnetic resonance spectrometer; the nuclear magnetic parameters of the obtained product are1H NMR(400MHz,CDCl3)δ11.15(s,1H),8.36(d,J＝8.7Hz,1H),7.90(d,J＝9.1Hz,1H),7.86(d,J＝8.4Hz,2H),7.70(d,J＝7.9Hz,1H),7.42-7.49(m,1H),7.29-7.34(m,1H),7.27(d,J＝8.3Hz,2H),7.17(d,J＝9.0Hz,1H),2.64(q,J＝7.6Hz,2H),1.18(t,J＝7.6Hz,3H).
Example 40: synthesis reaction of 1- (4-tert-butyl) benzenesulfonyl-2-naphthol
The dry clean sealed tube was charged with the iron-containing ionic liquid IL 4(20 mol%, 0.04mmol,17.9mg relative to 1a), followed by the addition of the reaction substrates β -naphthol (1a) (0.2mmol,28.8mg), (4-tert-butyl) phenyltriazene (2g) (0.3mmol,69.3mg) and DABCO (SO)2)2(3a) (0.24mmol,57.6mg), followed by addition of solvent CH3CN (2mL), the tube opening of the tube is sealed and the reaction is stirred for 14h at the temperature of 90 ℃. After completion of the reaction, 5mL of water was added to the reaction system to quench the reaction, and the aqueous mixture was extracted with ethyl acetate (3X 5mL, 3 times in total, 5mL each). After the extraction, the organic phase was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure, and isolated and purified by column chromatography (eluent: petroleum ether/ethyl acetate 50:1-30:1, v/v, (here 40:1)) to give an orange solid (53.1mg, 78%). Determining the obtained target product by adopting an infrared and nuclear magnetic resonance spectrometer; the nuclear magnetic parameters of the obtained product are1H NMR(400MHz,CDCl3)δ11.15(s,1H),8.41(d,J＝8.7Hz,1H),7.93(d,J＝9Hz,1H),7.91-7.86(m,2H),7.73(dd,J＝7.6,1.0Hz,1H),7.51-7.46(m,3H),7.35(m,1H),7.19(d,J＝9.0Hz,1H),1.28(s,9H).
Example 41: synthesis reaction of 1- (4-methoxy) benzenesulfonyl-2-naphthol
The dry clean lock tube was charged with the iron-containing ionic liquid IL 4(20 mol%, 0.04mmol,17.9mg relative to 1a), followed by the addition of the reaction substrates β -naphthol (1a) (0.2mmol,28.8mg), (4-methoxy) phenyltriazene (2h) (0.3mmol,61.6mg) and DABCO (SO)2)2(3a) (0.24mmol,57.6mg), followed by addition of solvent CH3CN (2mL), the tube opening of the tube is sealed and the reaction is stirred for 14h at the temperature of 90 ℃. After completion of the reaction, 5mL of water was added to the reaction system to quench the reaction, and the aqueous mixture was extracted with ethyl acetate (3X 5mL, 3 times in total, 5mL each). After the extraction, the organic phase was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure, and isolated and purified by column chromatography (eluent: petroleum ether/ethyl acetate 50:1-30:1, v/v, (here, 40:1)) to give an orange solid (50.3mg, 80%). Determining the obtained target product by adopting an infrared and nuclear magnetic resonance spectrometer; the nuclear magnetic parameters of the obtained product are1H NMR(400MHz,CDCl3)δ11.15(s,1H),8.36(d,J＝8.7Hz,1H),7.92-7.88(m,3H),7.71(d,J＝8.1Hz,1H),7.44-7.49(m,1H),7.30-7.36(m,1H),7.17(d,J＝9.0Hz,1H),6.93(d,J＝2.1Hz,1H),6.92(d,J＝2.1Hz,1H),3.80(s,3H).
Example 42: synthesis reaction of 1- (3-methylthio) benzenesulfonyl-2-naphthol
The dry clean sealed tube was charged with the iron-containing ionic liquid IL 4(20 mol%, 0.04mmol,17.9mg relative to 1a), followed by the addition of the reaction substrates β -naphthol (1a) (0.2mmol,28.8mg), (3-methylthio) phenyltriazene (2i) (0.3mmol,65.8mg) and DABCO (SO)2)2(3a) (0.24mmol,57.6mg), followed by addition of solvent CH3CN (2mL), the tube opening of the tube is sealed and the reaction is stirred for 14h at the temperature of 90 ℃. After completion of the reaction, 5mL of water was added to the reaction system to quench the reaction, and the aqueous mixture was extracted with ethyl acetate (3X 5mL, 3 times in total, 5mL each). After the extraction, the organic phase was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure, and separated and purified by column chromatography (eluent: petroleum ether/ethyl acetate 50:1-30:1, v/v, (here, 40:1)) to give an orange solid (35.7mg, 54%). Determining the obtained target product by adopting an infrared and nuclear magnetic resonance spectrometer; the nuclear magnetic parameters of the obtained product are1H NMR(400MHz,CDCl3)δ11.06(s,1H),8.34(d,J＝8.7Hz,1H),7.95(d,J＝9.0Hz,1H),7.80(t,J＝1.7Hz,1H),7.73(d,J＝8.0Hz,1H),7.66-7.62(m,1H),7.52-7.45(m,1H),7.38-7.33(m,3H),7.20(d,J＝9.1Hz,1H),2.48(s,3H).
Example 43: synthesis reaction of 4- (4-methyl) benzenesulfonylphenol
The dry clean sealed tube was charged with iron-containing ionic liquid IL 4(20 mol%, 0.04mmol,17.9mg relative to 1a), followed by the addition of the reaction substrates phenol (1b) (0.2mmol,18.8mg), (4-methyl) phenyltriazene (2a) (0.3mmol,56.7mg) and DABCO (SO)2)2(3a) (0.24mmol,57.6mg), followed by addition of solvent CH3CN (2mL), the tube opening of the tube is sealed and the reaction is stirred for 14h at the temperature of 90 ℃. After completion of the reaction, 5mL of water was added to the reaction system to quench the reaction, and the aqueous mixture was extracted with ethyl acetate (3X 5mL, 3 times in total, 5mL each). After the extraction, the organic phase was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure, and separated and purified by column chromatography (eluent: petroleum ether/ethyl acetate 50:1-30:1, v/v, (here, 40:1)) to give an orange liquid (17.9mg, 36%). Determining the obtained target product by adopting an infrared and nuclear magnetic resonance spectrometer; the nuclear magnetic parameters of the obtained product are1H NMR(400MHz,CDCl3)δ7.77(d,J＝8.7Hz,4H),δ7.27(d,J＝8.5Hz,2H),6.90(d,J＝8.8Hz,2H),6.60(s,1H),2.39(s,3H).
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (9)
1. A synthetic method of diaryl sulfone compounds is characterized in that:DABCO (SO) catalyzed by iron-containing Lewis acidic ionic liquid2)2As SO2The source uses aryltriazenes as aryl sources, realizes the sulphonation reaction of a beta-naphthol C1 site or a phenol C4 site, and obtains diaryl sulfone compounds (or diaryl sulfone derivatives).
2. The method of synthesis of claim 1, wherein: using aryltriazenes, beta-naphthols as donors for two aryl groups, DABCO (SO)2)2As SO2A source, which takes iron-containing ionic liquid as a catalyst to obtain a 1-benzenesulfonyl-2-naphthol compound (IV) in the following reaction formula; the reaction process is shown as the following reaction formula;
wherein R is1The substituent group is represented by one or more than two different positions of ortho-position, meta-position, para-position and the like of the benzene ring, the number of the substituent groups is 1-5, preferably 1-2, and the substituent groups can be specifically one or more than two of methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, methylthio and benzyl;
R2means that
One kind of (1).
3. The method of synthesis of claim 1, wherein: using aryltriazenes, phenol as donors for two aryl groups, DABCO (SO)2)2As SO2A source, which takes iron-containing ionic liquid as a catalyst to obtain a 4- (4-methyl) benzenesulfonyl phenol compound (VI) in the following reaction formula; the reaction process is shown as the following reaction formula;
4. a method of synthesis as claimed in claim 1,2 or 3, wherein: the iron-containing ionic liquid in the reaction is
One or more than two of them; the dosage of the iron-containing ionic liquid is 5 mol% -100 mol% of that of the beta-naphthol, preferably the dosage of the iron-containing ionic liquid is 15-30 mol% of that of the beta-naphthol, and more preferably the dosage of the iron-containing ionic liquid is 20 mol% of that of the beta-naphthol.
5. A method of synthesis as claimed in claim 1,2 or 3, wherein: the reaction is carried out in a solvent, the solvent is any one or two of acetonitrile and 1, 2-dichloroethane, and the preferable solvent is acetonitrile;
the concentration of beta-naphthol in the solvent is 0.1 to 0.2M, preferably the concentration of beta-naphthol in the solvent is 0.1 to 0.12M, more preferably the concentration of beta-naphthol in the solvent is 0.1M.
6. The method of synthesis of any of claims 1-5, wherein: in the reaction, beta-naphthol or phenol, aryltriazene, DABCO (SO)2)2The molar ratio of the amount of the compound is 1:1-1.5:0.8-1.2, preferably beta-naphthol or phenol, aryltriazene, DABCO (SO)2)2The molar ratio of the amount of the catalyst is 1:1.4-1.5:1.0-1.2, preferably 1:1.5: 1.2.
7. The method of synthesis of any of claims 1-6, wherein: the reaction comprises the following steps:
adding iron-containing ionic liquid, beta-naphthol or phenol, aryltriazene, and DABCO (SO) into a sealed container (such as a sealed tube)2)2And a solvent, and stirring and reacting under the condition of 40-100 ℃ (preferably 80-95 ℃, more preferably 90 ℃) to obtain the 1-arylsulfonyl-2-naphthol (IV) compound.
8. A method of synthesis as claimed in claim 1 or 2, characterized in that: the structure of the synthesized diaryl sulfone compound (or diaryl sulfone derivative) is shown as the formula (IV)
R1Is one or more of 2-methyl, 2, 6-dimethyl, 3-methyl, 3-methylthio, 4-methyl, 4-ethyl, 4-tert-butyl and 4-methoxy, and the number of the substituent groups is 1-5, preferably 1-2.
9. The method of synthesis of claim 7, wherein: the reaction time is 12-16h, preferably 13-15h, more preferably 14 h.
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| CN104045589A (en) * | 2014-05-07 | 2014-09-17 | 华东师范大学 | Aryl alkyl thioether compound and synthetic method thereof |
| CN106631926A (en) * | 2016-09-27 | 2017-05-10 | 华南理工大学 | Method for selectively compounding aryl methyl sulphone and belta-hydroxy sulphone derivative |
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| CN104045589A (en) * | 2014-05-07 | 2014-09-17 | 华东师范大学 | Aryl alkyl thioether compound and synthetic method thereof |
| CN106631926A (en) * | 2016-09-27 | 2017-05-10 | 华南理工大学 | Method for selectively compounding aryl methyl sulphone and belta-hydroxy sulphone derivative |
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| CN116836130B (en) * | 2023-08-31 | 2023-11-21 | 嘉实（湖南）医药科技有限公司 | Synthesis method of 3, 4-dihydrobenzothiadiazine compound |
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