CN110015942B - Method for directly synthesizing biaryl compound without metal catalysis - Google Patents
Method for directly synthesizing biaryl compound without metal catalysis Download PDFInfo
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- CN110015942B CN110015942B CN201910342958.1A CN201910342958A CN110015942B CN 110015942 B CN110015942 B CN 110015942B CN 201910342958 A CN201910342958 A CN 201910342958A CN 110015942 B CN110015942 B CN 110015942B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/30—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reactions not involving the formation of esterified sulfo groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
Abstract
The invention discloses a method for directly synthesizing biaryl hydrocarbon compounds without metal catalysis, which is characterized in that diaryl sulfoxide shown in a structural formula (I) reacts with trimethylsilyl phenyl trifluoromethanesulfonate shown in a structural formula (II) in the presence of cesium fluoride to obtain biaryl hydrocarbon compounds shown in a structural formula (III); the method provided by the invention does not need to add any expensive metal catalyst in the reaction process, reduces the preparation cost, and has better compatibility with substrates (such as halogen, OTs and the like) containing better leaving groups on aromatic rings.
Description
Technical Field
The invention belongs to the field of organic chemical synthesis, and particularly relates to a method for directly synthesizing biaryl compounds without metal catalysis.
Background
The biaryl compound has special optical and electrochemical properties, so that the biaryl compound can be widely applied to the fields of liquid crystal materials, organic functional materials, medicines, pesticides, organic synthetic intermediates and the like. Some biaryl compounds containing special functional groups (such as sulfydryl, nitro and the like) have received wide attention from wide scientists because of having special photoelectric properties. For example, the compound containing nitro can generate carbazole or polycarbazole with good photoelectric property through further reaction; the compound containing sulfydryl can form a self-assembled monomolecular film on the surface of metal such as gold, silver and the like, and the electronic device based on the conjugated organic film can be applied to the aspects of organic electroluminescent devices, organic negative resistance devices, molecular circuit devices, ultramicro chips, ultrahigh density information recording technology and the like. At present, the main method for synthesizing biaryl compounds is coupling reaction. However, the coupling reactions disclosed in the prior art all require the addition of expensive metal catalysts and have poor compatibility with substrates containing good leaving groups (e.g., halogens, OTs, etc.).
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a novel method for directly synthesizing biaryl compounds without metal catalysis, which has the advantages of mild reaction conditions, good selectivity, high yield, easy product separation, simple operation and the like.
In addition, more importantly, no expensive metal catalyst is required to be added in the whole reaction process, and the catalyst has excellent compatibility to the substrate containing halogen, OTs and other good leaving groups.
A method for directly synthesizing biaryl hydrocarbon compound without metal catalysis comprises the following steps of reacting diaryl sulfoxide shown in a structural formula (I) with trimethylsilyl phenyl trifluoromethanesulfonate shown in a structural formula (II) in the presence of cesium fluoride to obtain a biaryl hydrocarbon compound shown in a structural formula (III);
the structural formula (I), the structural formula (II) and the structural formula (III) are respectively as follows:
wherein: r1，R2Each independently selected from hydrogen, halogen, alkyl, alkoxycarbonyl, haloAlkyl, TsO-, cyano or nitro; ar (Ar)1，Ar2Selected from benzene ring and naphthalene ring.
Preferably, R is1，R2Each independently selected from hydrogen, F, Cl, Br, methyl, ethyl, isopropyl, tert-butyl, methoxycarbonyl, ethoxycarbonyl, F, Cl, B substituted methyl, F, Cl, B substituted ethyl, TsO-, cyano or nitro; as a further preference, the R group1，R2Each independently selected from hydrogen, Cl, Br, trifluoromethyl, TsO-and cyano.
Preferably, the molar ratio of diaryl sulfoxide to trimethylsilylphenyl triflate is 1: (1-5). More preferably 1: (2.5-4.5).
Preferably, the molar ratio of diaryl sulfoxide to cesium fluoride is 1: (1-5). More preferably 1: (2.5-4.5).
Preferably, the reaction solvent is one or more of dichloromethane, chloroform, acetonitrile and acetone.
Preferably, the reaction temperature is 20 to 40 ℃.
Preferably, the trimethylsilyl phenyl trifluoromethanesulfonate or cesium fluoride is added in portions.
Preferably, the reaction time is 12-48 hours, 1/2 parts of the total amount of trimethylsilyl phenyl trifluoromethanesulfonate or cesium fluoride is added in the initial stage, 1/4 parts of the total amount of trimethylsilyl phenyl trifluoromethanesulfonate or cesium fluoride are added in the total time of 1/3, and the rest of trimethylsilyl phenyl trifluoromethanesulfonate or cesium fluoride is added in the total time of 2/3.
Preferably, the diaryl sulfoxide is selected from one or more of the following compounds:
according to the method provided by the invention, after the reaction is finished, the product with the purity of more than 99% can be obtained through filtration and column chromatography, and the post-treatment is simple.
Compared with the prior art, the invention has the beneficial effects that:
the method provided by the invention does not need to add any expensive metal catalyst in the reaction process, reduces the preparation cost, and has better compatibility with substrates (such as halogen, OTs and the like) containing better leaving groups on aromatic rings.
The method provided by the invention has the advantages of mild reaction conditions, good selectivity, high yield, easy product separation and simple operation, and the used raw materials can be purchased from commercial products, are wide in source and have better economical efficiency in the whole process.
Detailed Description
Example 1
N2Under protection, redistilled acetonitrile (2.5mL) was added to a 25mL reaction tube, and then 76mg (0.5mmol) of cesium fluoride was added, followed by p-chlorinated diphenyl sulfoxide (68mg,0.25mmol) and trimethylsilyl phenyl triflate (149.2mg,0.5mmol), and the reaction was stirred at room temperature for 36 hours. During this reaction, cesium fluoride (38.0mg,0.25mmol) and trimethylsilylphenyltrifluoromethanesulfonate (74.6mg,0.25mmol) were added further at 12 hours and 24 hours, respectively. Tracking the reaction process by thin layer chromatography, filtering and concentrating after the reaction is finished, and separating by column chromatography to obtain 45.2mg of product, wherein the yield is 81%, and the purity is more than 99%. The target product is a known compound, and the obtained nuclear magnetic spectrum data is consistent with the literature report. (p.puthiraj, p.suresh, and k.pitchumani, green.chem.2014,16,2865):
1H NMR(600MHz,CDCl3):δ7.56–7.53(m,4H),7.41–7.38(m,4H)。
example 2
N2Under protection, redistilled acetonitrile (2.5mL) was added to a 25mL reaction tube, and then 76mg (0.5mmol) of cesium fluoride was added, followed by p-brominated diphenyl sulfoxide (60mg,0.25mmol) and trimethylsilylphenyl triflate (149.2mg,0.5mmol), and the reaction was stirred at room temperature for 36 hours. During this reaction, cesium fluoride (38.0mg,0.25mmol) and trimethylsilylphenyltrifluoromethanesulfonate (74.6mg,0.25mmol) were added further at 12 hours and 24 hours, respectively. The reaction process is followed by thin layer chromatography, after the reaction is finished, filtration and concentration are carried out, and the product of 57.7mg is obtained through column chromatography separation, wherein the yield is 74 percent, and the purity is more than 99 percent. The target product is a known compound, and the obtained nuclear magnetic spectrum data is consistent with the literature report. (p.puthiraj, p.suresh, and k.pitchumani, green.chem.2014,16,2865):
1H NMR(600MHz,CDCl3):δ7.58–7.41(m,4H),7.15–7.10(m,4H)。
example 3
N2Under protection, redistilled acetonitrile (2.5mL) was added to a 25mL reaction tube, and then 76mg (0.5mmol) of cesium fluoride was added, followed by the addition of p-OTs substituted diphenyl sulfoxide (136mg,0.25mmol) and trimethylsilylphenyl triflate (149.2mg,0.5mmol), and the reaction was stirred at room temperature for 36 hours. During this reaction, cesium fluoride (38.0mg,0.25mmol) and trimethylsilylphenyltrifluoromethanesulfonate (74.6mg,0.25mmol) were added further at 12 hours and 24 hours, respectively. Tracking reaction process by thin layer chromatography, filtering, concentrating, and separating by column chromatography to obtain 65.5mg product with yield of 53% and purity of more than 99%. The target product was a white solid with a melting point of 190-.
1H NMR(600MHz,CDCl3):δ7.73(d,J＝8.3Hz,4H),7.45–7.40(m,4H),7.32(d,J＝8.1Hz,4H),7.06–7.01(m,4H),2.45(s,6H).
13C NMR(151MHz,CDCl3):δ149.3,145.6,138.9,132.5,130.0,128.7,128.4,123.0,21.9.
IR(neat):3044,2922,2162,1980,1736,1597,1490,1220,1088,1043,944,853.
HRMS(ESI-TOF):calculated for[C26H22O6S2Na(M+Na+)]:517.0750,found:517.0730.
Example 4
N2Under protection, redistilled acetonitrile (2.5mL) was added to a 25mL reaction tube, and then 76mg (0.5mmol) of cesium fluoride was added, followed by addition of p-trifluoromethyl substituted diphenyl sulfoxide (85mg,0.25mmol) and trimethylsilylphenyltrifluoromethanesulfonate (149.2mg,0.5mmol), and the reaction was stirred at room temperature for 36 hours. During this reaction, cesium fluoride (38.0mg,0.25mmol) and trimethylsilylphenyltrifluoromethanesulfonate (74.6mg,0.25mmol) were fed in at 12 hours and 24 hours, respectively. Tracking reaction process with thin layer chromatography, filtering, concentrating, and separating by column chromatography to obtain product 61.2mg, yield 83%, and purity greater than 99%. The target product is a known compound, and the obtained nuclear magnetic spectrum data is consistent with the literature report. (t.korenaga, k.nitatori, h.muraoka, s.ogawa and k.shimada, org.lett.2015,17,5500):
1H NMR(600MHz,CDCl3):δ7.74(d,J＝8.4Hz,4H),7.70(d,J＝8.3Hz,4H)。
example 5
N2Under protection, redistilled acetonitrile (2.5mL) was added to a 25mL reaction tube, and then 76mg (0.5mmol) of cesium fluoride was added, followed by p-carbomethoxy-substituted diphenyl sulfoxide (83mg,0.25mmol) and trimethylsilylphenyl trifluoromethanesulfonate (149.2mg,0.5mmol), and the reaction solution was stirred at room temperature for 36 hours.During this reaction, cesium fluoride (38.0mg,0.25mmol) and trimethylsilylphenyltrifluoromethanesulfonate (74.6mg,0.25mmol) were added further at 12 hours and 24 hours, respectively. Tracking the reaction process by thin layer chromatography, filtering and concentrating after the reaction is finished, and separating by column chromatography to obtain 47.3mg of product, wherein the yield is 70%, and the purity is more than 99%. The target product is a known compound, and the obtained nuclear magnetic spectrum data is consistent with the literature report. (t.yurino, y.ueda, y.shimizu, s.tanaka, h.nishiyama, h.tsuugi, k.sato, k.mashima, angelw.chem.int.ed.2015, 54,14437):
1H NMR(600MHz,CDCl3):δ8.22–8.05(m,4H),7.79–7.59(m,4H),3.95(s,6H)。
example 6
N2Under protection, redistilled acetonitrile (2.5mL) was added to a 25mL reaction tube, and then 76mg (0.5mmol) of cesium fluoride was added, followed by addition of p-cyano substituted diphenyl sulfoxide (63mg,0.25mmol) and trimethylsilylphenyl triflate (149.2mg,0.5mmol), and the reaction was stirred at room temperature for 36 hours. During this reaction, cesium fluoride (38.0mg,0.25mmol) and trimethylsilylphenyltrifluoromethanesulfonate (74.6mg,0.25mmol) were added further at 12 hours and 24 hours, respectively. Tracking the reaction process by thin layer chromatography, filtering and concentrating after the reaction is finished, and separating by column chromatography to obtain 40.8mg of product, wherein the yield is 80%, and the purity is more than 99%. The target product is a known compound, and the obtained nuclear magnetic spectrum data is consistent with the literature report. (p.puthiraj, p.suresh, and k.pitchumani, green.chem.2014,16,2865):
1H NMR(600MHz,CDCl3):δ7.78–7.76(m,4H),7.70–7.67(m,4H).
example 7
N2Redistilled acetonitrile (2.5mL) was added to 25m with protectionIn a reaction tube of l, 76mg (0.5mmol) of cesium fluoride was further added, followed by addition of p-cyano, bromo-substituted diphenylsulfoxide (77mg,0.25mmol) and trimethylsilylphenyltrifluoromethanesulfonate (149.2mg,0.5mmol), and the reaction solution was stirred at room temperature for 36 hours. During this reaction, cesium fluoride (38.0mg,0.25mmol) and trimethylsilylphenyltrifluoromethanesulfonate (74.6mg,0.25mmol) were added further at 12 hours and 24 hours, respectively. Tracking reaction process by thin layer chromatography, filtering, concentrating, and separating by column chromatography to obtain 49.7mg product with yield of 77% and purity of more than 99%. The target product is a known compound, and the obtained nuclear magnetic spectrum data is consistent with the literature report. (m.lindner, m.valsek, m.mayor, t.frauhammer, w.wulfhekel, l.gerhard, angelw.chem.int.ed.2017, 56,8290):
1H NMR(600MHz,CDCl3):δ7.73(d,J＝8.2Hz,2H),7.65(d,J＝8.2Hz,2H),7.61(d,J＝8.3Hz,2H),7.45(d,J＝8.3Hz,2H).
example 8
N2Under protection, redistilled acetonitrile (2.5mL) was added to a 25mL reaction tube, and then 76mg (0.5mmol) of cesium fluoride was added, followed by dinaphthyl sulfoxide (76mg,0.25mmol) and trimethylsilyl phenyl trifluoromethanesulfonate (149.2mg,0.5mmol), and the reaction was stirred at room temperature for 36 hours. During this reaction, cesium fluoride (38.0mg,0.25mmol) and trimethylsilylphenyltrifluoromethanesulfonate (74.6mg,0.25mmol) were added further at 12 hours and 24 hours, respectively. Tracking the reaction process by thin layer chromatography, filtering and concentrating after the reaction is finished, and separating by column chromatography to obtain 36.2mg of product, wherein the yield is 57%, and the purity is more than 99%. The target product is a known compound, and the obtained nuclear magnetic spectrum data is consistent with the literature report. (r.a.novikov, a.v.tarasova, d.a.denisov, d.d.borisov, v.a.korolev, v.p.timofev, y.v.tomlov, j.org.chem.2017,82,2724.):
1H NMR(600MHz,CDCl3):δ7.98–7.93(m,4H),7.62–7.57(m,2H),7.51–7.49(m,2H),7.49–7.45(m,2H),7.39(d,J＝8.4Hz,2H),7.31–7.27(m,2H)。
Claims (5)
1. a method for directly synthesizing biaryl hydrocarbon compound without metal catalysis is characterized in that diaryl sulfoxide shown in a structural formula (I) reacts with trimethylsilyl phenyl trifluoromethanesulfonate shown in a structural formula (II) in the presence of cesium fluoride to obtain biaryl hydrocarbon compound shown in a structural formula (III);
the structural formula (I), the structural formula (II) and the structural formula (III) are respectively as follows:
wherein: r1，R2Each independently selected from Cl, Br, trifluoromethyl, methoxycarbonyl, TsO-and cyano; ar (Ar)1，Ar2Selected from benzene ring and naphthalene ring;
or the diaryl sulfoxide shown in the structural formula (I) is dinaphthyl sulfoxide;
the molar ratio of diaryl sulfoxide to trimethylsilyl phenyl trifluoromethanesulfonate is 1: 3;
the trimethylsilyl phenyl triflate or cesium fluoride is added in batches:
the reaction time is 12-48 hours, 1/2 of the total amount of trimethylsilyl phenyl trifluoromethanesulfonate and cesium fluoride is added in the initial stage, 1/4 of the total amount of trimethylsilyl phenyl trifluoromethanesulfonate and cesium fluoride is added in the total time of 1/3, and the rest of trimethylsilyl phenyl trifluoromethanesulfonate and cesium fluoride are added in the total time of 2/3.
2. The metal-free catalytic direct synthesis of a biaryl compound according to claim 1, wherein the molar ratio of diaryl sulfoxide to cesium fluoride is 1: (1-5).
3. The method for directly synthesizing biaryl compounds without metal catalysis according to claim 1, wherein the reaction solvent is one or more of dichloromethane, chloroform, acetonitrile and acetone.
4. The method for directly synthesizing biaryl compounds without metal catalysis according to claim 1, wherein the reaction temperature is 20-40 ℃.
5. The metal-free catalyzed direct synthesis of biaryl compounds according to claim 1, wherein the diaryl sulfoxide is selected from the group consisting of:
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1871212A (en) * | 2003-10-21 | 2006-11-29 | 和光纯药工业株式会社 | Process for producing triarylsulfonium salt |
| CN106892848A (en) * | 2017-01-20 | 2017-06-27 | 浙江师范大学 | A kind of new method for preparing triaryl sulfonium salts |
| CN106946751A (en) * | 2017-03-03 | 2017-07-14 | 浙江师范大学 | A kind of method for preparing diaryl sulfide |
| CN109134332A (en) * | 2017-06-15 | 2019-01-04 | 浙江师范大学 | A method of triaryl sulfonium salts are prepared by diaryl sulfide arylation |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1871212A (en) * | 2003-10-21 | 2006-11-29 | 和光纯药工业株式会社 | Process for producing triarylsulfonium salt |
| CN106892848A (en) * | 2017-01-20 | 2017-06-27 | 浙江师范大学 | A kind of new method for preparing triaryl sulfonium salts |
| CN106946751A (en) * | 2017-03-03 | 2017-07-14 | 浙江师范大学 | A kind of method for preparing diaryl sulfide |
| CN109134332A (en) * | 2017-06-15 | 2019-01-04 | 浙江师范大学 | A method of triaryl sulfonium salts are prepared by diaryl sulfide arylation |
Non-Patent Citations (3)
| Title |
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| Nickel-Catalyzed Cross-Coupling Reaction of Aryl Sulfoxides with Arylzinc Reagents: A Case that Leaving Group is an Oxidant;Keita Yamamoto et al;《ACS CATALYSIS》;20170928;第1-23页 * |
| Oxidation-State-Dependent Photochemistry of Sulfur-Bridged Anthracenes;Peter R. Christensen et al;《Angew. Chem. Int. Ed.》;20131231;第52卷;第12946-12950页 * |
| Synthesis of o‑Aryloxy Triarylsulfonium Salts via Aryne Insertion intoDiaryl Sulfoxides;Xiaojin Li et al;《organic letters》;20170217;第19卷(第4期);第838-841页 * |
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