CN114149405B - Method for synthesizing aromatic thioether through aromatic exchange bimetallic catalysis and application thereof - Google Patents

Method for synthesizing aromatic thioether through aromatic exchange bimetallic catalysis and application thereof Download PDF

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CN114149405B
CN114149405B CN202111255310.4A CN202111255310A CN114149405B CN 114149405 B CN114149405 B CN 114149405B CN 202111255310 A CN202111255310 A CN 202111255310A CN 114149405 B CN114149405 B CN 114149405B
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黄辉
史钦钦
梁新宇
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Abstract

The invention discloses a method for synthesizing aromatic thioether through aromatic exchange bimetallic catalysis and application thereof, wherein the method adopts inert gas for protection, and 1-1' -bis (diphenylphosphine) ferrocene (dppf), dipotassium hydrogen phosphate, zn powder and Zn powder are added under the action of a double catalyst of palladium acetate and 1, 2-bis (diphenylphosphine) ethane nickel chlorideThe molecular sieve is used as an additive, aryl halide or other aryl electrophile and aryl thioether source are placed in dimethylacetamide, and the reaction is carried out at the temperature of 100 ℃ to obtain the aromatic thioether. Adding saturated sodium chloride solution into the reaction system to quench the reaction, extracting the organic phase with dichloromethane three times, removing water from the organic phase with anhydrous sodium sulfate, removing the organic solvent under reduced pressure, and passing through a rapid column chromatography to obtain a pure product. The method can be applied to the field of preparing organic field effect transistor materials and medicines.

Description

Method for synthesizing aromatic thioether through aromatic exchange bimetallic catalysis and application thereof
Technical Field
The invention belongs to the technical field of aromatic thioether synthesis, and particularly relates to a method for synthesizing aromatic thioether through aromatic exchange bimetallic catalysis and application thereof.
Background
Aryl sulfides, particularly aryl methyl sulfides, are of great interest because of their wide-spread presence in natural products, such as Roseochelin B, macrophilone a and olismin a are all naturally occurring aryl methyl sulfides. In addition, many drugs also contain arylmethyl sulfide. Meanwhile, in the field of organic semiconductors, aryl sulfide is a relatively excellent organic semiconductor material and has excellent performance in the field of field effect transistors and the like. Finally, in the Liebeskind-Srogl reaction, aryl sulfide is reacted as a leaving group with an organometallic reagent to build a C-C bond. Thus, the synthesis of arylthiomethyl ethers has been a focus of research in the field of organic synthesis.
The general synthesis method of aryl sulfide is that aryl mercaptan is used as a thioether source and reacts with aryl halide under the catalysis of transition metal to generate aryl sulfide, or aryl compound is used for generating lithium salt under the action of n-butyl lithium and then reacts with disulfide to generate aryl sulfide. Aryl thiols have three disadvantages of malodor, slight toxicity, and susceptibility to self-polymerization. Therefore, development of a method for synthesizing aryl sulfide without using thiol as a sulfide source has been a hot spot of research by scientists. Recently, scientists have synthesized aryl sulfides using dimethyl sulfoxide as a sulfide source and a reaction solvent, but the reaction temperature of the system is high and the substrate is limited. Recently, it has been reported that a C-S bond is formed by using pyridine sulfide as a sulfide source, but the reaction activity of methyl sulfide is not high in its reaction system. In addition, benzothiazole methyl sulfide is a compound present in urban runoff sewage, and currently, a subject group aims to convert the benzothiazole methyl sulfide into an organic semiconductor material, so that valuable conversion is realized.
By searching, no patent publication related to the present patent application has been found.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a method for synthesizing aromatic thioether through aromatic exchange bimetallic catalysis and application thereof.
The technical scheme adopted for solving the technical problems is as follows:
a method for synthesizing aromatic thioether through aromatic exchange bimetallic catalysis, which takes benzothiazole methyl sulfide as a thioether source and takes aryl electrophile as a thioether acceptor, prepares aryl thioether under the condition of catalyst/alkali/reducing agent/solvent, wherein the catalyst is palladium acetate and 1, 2-bis (diphenylphosphine) ethane nickel chloride, and the reaction general formula is shown as follows:
LG：Br，I，Cl，OTf，OMs，OTs，COCl，SO 2 Cl，CO 2 R
wherein Ar is 1 And Ar is a group 2 Represents identical or different aryl systems.
Further, the aryl electrophile is any one of the following compounds:
wherein LG is Br, I, cl, OTf, OMs, OTs, COCl, SO 2 Cl,CO 2 R；
Wherein R, R 1 ,R 2 Is independent C 1 -C 15 Including straight chain alkyl groups having a total of 1 to 15 carbon atoms including: n-methyl, n-ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl; branched alkyl groups having a total number of carbon atoms of 3 to 15 include: isopropyl, 2-methylpropyl, 2-methylbutyl, 3-ethylbutyl, 2-methylpentyl, 2-methylhexyl, 2-methylheptyl, 2-methyloctyl, 2-methylnonyl, 2-methyldecyl, 2-methylundecyl, 2-methyldodecyl, 2-methyltridecyl, 2-methyltetradecyl, 3-ethylpentyl, 3-ethylhexyl, 3-ethylheptyl, 3-ethyloctyl, 3-ethylnonyl, 3-ethyldecyl, 3-ethylundecyl, 3-ethyldodecyl, 3-ethyltridecyl.
Further, the benzothiazole methyl sulfide is any one of the following compounds:
further, the method comprises the following specific steps:
(1) In Pd (OAc) under inert gas protection 2 ，Ni(dppe)Cl 2 Adding dppf and dipotassium hydrogen phosphate as additives, activated Zn powder as reducing agent, and dryingMS molecular sieve, putting thioether acceptor aryl electrophile and aryl thioether source into dimethylacetamide, and reacting to obtain a mixture;
(2) Dropping saturated sodium chloride solution into the mixture to quench, extracting with dichloromethane for three times, removing water from the organic phase through anhydrous sodium sulfate, removing the organic solvent under reduced pressure, and purifying by a rapid column chromatography to obtain the product.
Further, the aryl electrophile and benzothiazole methyl sulfide achieve a sulfide exchange reaction at 100 ℃.
Further, the method is based on an aryl thioether source with an aryl electrophile in Pd (OAc) 2 And Ni (dppe) Cl 2 The method is realized under the combined catalysis, and comprises the following specific synthesis methods:
1.0 equivalent of an aryl thioether source, 1.0 equivalent of an aryl electrophile, 10.0 mole% Pd (OAc) 2 10.0mol% Ni (dppe) Cl 2 10.0mol% of 1-1' -bis (diphenylphosphorus) ferrocene, 2.0 equivalents of dipotassium hydrogen phosphate and 2.5 equivalents of zinc powder were placed in a reaction flask; after three nitrogen substitutions, dry dimethylacetamide was added to maintain the concentration of the solution at 0.1M, and dryA molecular sieve; stirring at 100deg.C for 12 hr, and reversingAdding saturated sodium chloride solution into the reaction system to quench the reaction, extracting the organic phase with dichloromethane for three times, removing water from the organic phase through anhydrous sodium sulfate, removing the organic solvent under reduced pressure, and obtaining a pure product through a rapid column passing machine.
The use of the method as described above in the preparation of organic field effect transistor materials.
The use of the method as described above in the preparation of a medicament.
The use of the method as described above in the preparation of an organic semiconductor material.
The invention has the advantages and positive effects that:
1. the method avoids the use of mercaptan in the reaction process and reduces the generation of malodorous smell.
2. The method of the invention avoids the use of mercaptan in the reaction process and avoids the influence of yield loss caused by mercaptan self-polymerization.
3. The process of the invention avoids the use of mercaptans during the reaction and avoids the slight toxicity of mercaptans.
4. The method uses benzothiazole thiomethyl ether as a thioether source in the reaction process, successfully synthesizes a drug and an organic semiconductor material, and fully utilizes wastes.
5. The method can be applied to a reaction system with more than one gram in the reaction process to obtain the yield equivalent to micro-reaction.
6. The invention relates to an aryl thioether exchange reaction based on Ni and Pd co-catalysis at 100 ℃, which adopts inert gas protection, under the action of a double catalyst of palladium acetate and 1, 2-bis (diphenylphosphine) ethane nickel chloride, 1-1' -bis (diphenylphosphine) ferrocene (dppf), dipotassium hydrogen phosphate, zn powder andthe molecular sieve is used as an additive, aryl halide or other aryl electrophile and aryl thioether source are placed in dimethylacetamide, and the reaction is carried out at the temperature of 100 ℃ to obtain the aromatic thioether. Into the reaction systemThe reaction was quenched by addition of saturated sodium chloride solution, then the organic phase was extracted three times with dichloromethane, the organic phase was dehydrated over anhydrous sodium sulfate, then the organic solvent was removed under reduced pressure, and the pure product was obtained by rapid column chromatography. The method can be applied to the field of preparing organic field effect transistor materials and medicines.
Drawings
FIG. 1 is a graph of UV absorption and cyclic voltammogram of an organic semiconductor material in accordance with the present invention; wherein a and d are respectively ultraviolet absorption patterns of 5a and 5b in chloroform (solution) and film (film), and b and e are respectively 5a and 5b in CH 2 Cl 2 /0.1M[nBu 4 N] + [PF 6 ] - In the solution, ferrocene is used as a Cyclic Voltammogram (CV) of an internal standard, c and f are Cyclic Voltammograms (CV) of ferrocene, and (b), and (c), and (e) and (f) are all from the same experimental environment, and only Ag wires coated with AgCl are used as reference electrodes;
FIG. 2 is a graph showing the thermal performance characteristics of an organic semiconductor material according to the present invention; wherein a: TGA curve of 5 a), b): DSC curve of 5a, c:5b, d: DSC profile of 5 b.
Detailed Description
The following describes the embodiments of the present invention in detail, but the present embodiments are illustrative and not limitative, and are not intended to limit the scope of the present invention.
The raw materials used in the invention are conventional commercial products unless specified; the methods used in the present invention are conventional in the art unless otherwise specified.
A method for synthesizing aromatic thioether through aromatic exchange bimetallic catalysis, which takes benzothiazole methyl sulfide as a thioether source, takes aryl halide or aryl electrophile except the aryl halide as a thioether acceptor, and prepares the aryl thioether under the condition of catalyst/alkali/reducing agent/solvent, wherein the catalyst is palladium acetate and 1, 2-bis (diphenylphosphine) ethane nickel chloride, and the reaction general formula is shown as follows:
LG：Br，I，Cl，OTf，OMs，OTs，COCI，SO 2 CI，CO 2 R
wherein Ar is 1 And Ar is a group 2 Represents identical or different aryl systems.
Preferably, the aryl electrophile is any one of the following compounds:
wherein LG is Br, I, cl, OTf, OMs, OTs, COCl, SO 2 Cl,CO 2 R；
Wherein R, R 1 ,R 2 Is independent C 1 -C 15 Including straight chain alkyl groups having a total of 1 to 15 carbon atoms including: n-methyl, n-ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl; branched alkyl groups having a total number of carbon atoms of 3 to 15 include: isopropyl, 2-methylpropyl, 2-methylbutyl, 3-ethylbutyl, 2-methylpentyl, 2-methylhexyl, 2-methylheptyl, 2-methyloctyl, 2-methylnonyl, 2-methyldecyl, 2-methylundecyl, 2-methyldodecyl, 2-methyltridecyl, 2-methyltetradecyl, 3-ethylpentyl, 3-ethylhexyl, 3-ethylheptyl, 3-ethyloctyl, 3-ethylnonyl, 3-ethyldecyl, 3-ethylundecyl, 3-ethyldodecyl, 3-ethyltridecyl.
Preferably, the benzothiazole methyl sulfide is any one of the following compounds:
preferably, the specific steps are:
(1) In Pd (OAc) under inert gas protection 2 ，Ni(dppe)Cl 2 Catalytic action of (2)The following were added dppf and dipotassium hydrogen phosphate as additives, activated Zn powder as reducing agent, and driedMS molecular sieve, putting thioether acceptor aryl electrophile and aryl thioether source into dimethylacetamide, and reacting to obtain a mixture;
(2) Dropping saturated sodium chloride solution into the mixture to quench, extracting with dichloromethane for three times, removing water from the organic phase through anhydrous sodium sulfate, removing the organic solvent under reduced pressure, and purifying by a rapid column chromatography to obtain the product.
Preferably, the aryl electrophile and benzothiazole methyl sulfide effect a sulfide exchange reaction at 100 ℃.
Preferably, the method is based on an aryl thioether source with an aryl electrophile in Pd (OAc) 2 And Ni (dppe) Cl 2 The method is realized under the combined catalysis, and comprises the following specific synthesis methods:
1.0 equivalent of an aryl thioether source, 1.0 equivalent of an aryl electrophile, 10.0 mole% Pd (OAc) 2 10.0mol% Ni (dppe) Cl 2 10.0mol% of 1-1' -bis (diphenylphosphorus) ferrocene, 2.0 equivalents of dipotassium hydrogen phosphate and 2.5 equivalents of zinc powder were placed in a reaction flask; after three nitrogen substitutions, dry dimethylacetamide was added to maintain the concentration of the solution at 0.1M, and dryA molecular sieve; stirring at 100deg.C for 12 hr, adding saturated sodium chloride solution into the reaction system, quenching, extracting the organic phase with dichloromethane for three times, removing water from the organic phase with anhydrous sodium sulfate, removing the organic solvent under reduced pressure, and passing through quick column chromatography to obtain the final product.
The use of the method as described above in the preparation of organic field effect transistor materials.
The use of the method as described above in the preparation of a medicament.
The use of the method as described above in the preparation of an organic semiconductor material.
Specifically, the relevant preparation and detection examples are as follows:
example 1
1.0 equivalent of benzothiazole methyl sulfide (0.2 mmol,36.2 mg), 1.0 equivalent of 2-bromo-3-hexylthiophene (0.2 mmol,49.4 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated through anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a colorless liquid (36.6 mg, 86%) was obtained by rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.25(d,J＝5.0Hz,1H),6.90(d,J＝5.0Hz,1H),2.69(t,J＝7.5Hz,2H),2.38(s,3H),1.60-1.54(m,2H),1.36-1.26(m,6H),0.90(t,J＝7.0Hz,3H)。 13 C NMR(126MHz,CDCl 3 )δ146.48,130.35,128.93,126.98,31.82,30.85,29.23,29.01,22.76,22.39,14.25。GCMS m/z calcd for C 11 H 18 S 2 [M] + :214.08 found 214。
Example 2
1.0 equivalent of benzothiazole methyl sulfide (0.2 mmol,36.2 mg), 1.0 equivalent of 2-bromothiophene (0.2 mmol,32.8 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalentsZinc powder (0.5 mmol,32.5 mg) was placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated through anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a colorless liquid (21.1 mg, 81%) was obtained by rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.31(d,J＝5.5Hz,1H),7.09(d,J＝3.5Hz,1H),6.98(t,J＝3.5Hz,1H),2.50(s,3H)。 13 C NMR(126MHz,CDCl 3 )δ137.20,131.12,128.02,127.54,22.34。
Example 3
8.0 equivalents of benzothiazole dimethyl sulfide (1.6 mmol,289.6 mg), 1.0 equivalents of 3,3 '-dibromo-2, 2' -dithiophene (0.2 mmol,64.6 mg), pd (OAc) 2 (0.04 mmol,9.0 mg) and Ni (dppe) Cl 2 (0.04 mmol,21.2 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.04 mmol,22.2 mg), 4.0 equivalents of dipotassium hydrogen phosphate (0.8 mmol,140.0 mg) and 5.0 equivalents of zinc powder (1.0 mmol,65.0 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (5.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated through anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and white powder (35.4 mg, 69%) was obtained by passing through a rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.36(d,J＝5.3Hz,2H),7.05(d,J＝5.3Hz,2H),2.38(s,6H)。 13 C NMR(126MHz,CDCl 3 )δ136.3,130.4,128.7,127.0,15.8。
Example 4
1.0 equivalent of benzothiazole methyl sulfide (0.2 mmol,36.2 mg)1.0 equivalent of bromobenzene (0.2 mmol,31.2 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated over anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a colorless liquid (18.8 mg, 76%) was obtained by rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.33-7.28(m,4H),7.19-7.15(m,1H),2.51(s,3H)。 13 C NMR(126MHz,CDCl 3 )δ138.48,128.89,126.62,125.06,15.87。
Example 5
1.0 equivalent of benzothiazole methyl sulfide (0.2 mmol,36.2 mg), 1.0 equivalent of 1-bromo-4-methylbenzene (0.2 mmol,34.0 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated through anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a colorless liquid (22.9 mg, 83%) was obtained by rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.22(d,J＝8.0Hz,2H),7.14(d,J＝8.0Hz,2H),2.49(s,3H),2.35(s,3H)。 13 C NMR(126MHz,CDCl 3 )δ135.08,134.78,129.68,127.31,20.98,16.56。
Example 6
1.0 equivalent of benzothiazole dimethyl sulfide (0.2 mmol,36.2 mg), 1.0 equivalent of 4-bromo-1, 2-dimethylbenzene (0.2 mmol,36.8 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated over anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a colorless liquid (25.5 mg, 84%) was obtained by rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.09(d,J＝4.0Hz,1H),7.06(s,1H),7.05(d,J＝8.0Hz,1H),2.47(s,3H),2.25(s,3H),2.23(s,3H)。 13 C NMR(126MHz,CDCl 3 )δ137.35,134.98,133.94,130.24,128.69,124.80,19.90,19.38,16.64。
Example 7
1.0 equivalent of benzothiazole methyl sulfide (0.2 mmol,36.2 mg), 1.0 equivalent of 1-bromo-4-methoxybenzene (0.2 mmol,37.2 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated through anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a yellow liquid (24.7 mg, 80%) was obtained by passing through a rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.27(d,J＝9.0Hz,2H),6.85(d,J＝9.0Hz,2H),3.78(s,3H),2.44(s,3H)。 13 C NMR(126MHz,CDCl 3 )δ158.30,130.30,128.86,114.72,55.50,18.22。
Example 8
1.0 equivalent of benzothiazole dimethyl sulfide (0.2 mmol,36.2 mg), 1.0 equivalent of 4-bromo-1, 2-dimethoxybenzene (0.2 mmol,43.2 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated over anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a yellow solid (30.6 mg, 83%) was obtained by passing through a rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ6.41(s,2H),6.24(s,1H),3.78(s,6H),2.47(s,3H)。 13 C NMR(126MHz,CDCl 3 )δ161.06,140.74,104.42,97.44,55.49,15.70。
Example 9
1.0 equivalent of benzothiazole methyl sulfide (0.2 mmol,36.2 mg), 1.0 equivalent of 4-bromo-1, 1' -biphenyl (0.2 mmol,46.4 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring for 12 hours at 100 deg.c,a saturated sodium chloride solution was added to the reaction system to quench the reaction, then an organic phase was extracted three times with methylene chloride, the organic phase was dehydrated by anhydrous sodium sulfate, then the organic solvent was removed under reduced pressure, and a colorless liquid (35.0 mg, 88%) was obtained by rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.58(d,J＝7.0Hz,2H),7.54(d,J＝8.5Hz,2H),7.45(t,J＝7.5Hz,2H),7.36-7.33(m,3H),2.53(s,3H)。 13 C NMR(126MHz,CDCl 3 )δ140.64,138.12,137.69,128.94,127.61,127.33,127.01,126.96,16.00。
Example 10
1.0 equivalent of benzothiazole methyl sulfide (0.2 mmol,36.2 mg), 1.0 equivalent of 1-bromo-4-butylbenzene (0.2 mmol,42.4 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated through anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a colorless liquid (30.6 mg, 85%) was obtained by rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.20(d,J＝8.5Hz,2H),7.11(d,J＝8.5Hz,2H),2.57(t,2H),2.47(s,3H),1.60-1.54(m,2H),1.38-1.28(m,2H),0.92(t,J＝7.5Hz,3H)。 13 C NMR(126MHz,CDCl 3 )δ140.25,134.99,129.12,127.26,35.24,33.77,22.44,16.56,14.10。
Example 11
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1.0 equivalent of benzothiazole dimethyl sulfide (0.2 mmol,36.2 mg), 1.0 equivalent of 1-bromo-o-methyl sulfide4-fluorobenzene (0.2 mmol,34.8 mg), pd (OAc) 2 (0.02 mmol,4.49 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated over anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a yellow solid (24.2 mg, 85%) was obtained by passing through a rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.27-7.24(m,2H),7.00(t,J＝8.5Hz,2H),2.47(s,3H)。 13 C NMR(126MHz,CDCl 3 )δ162.21,160.26,133.41,129.34,116.14,115.96,17.23。
Example 12
1.0 equivalent of benzothiazole methyl sulfide (0.2 mmol,36.2 mg), 1.0 equivalent of 1-bromo-4-trifluoromethylbenzene (0.2 mmol,44.8 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated over anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a colorless liquid (28.7 mg, 76%) was obtained by rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.52(d,J＝8.0Hz,2H),7.31(d,J＝8.5Hz,2H),2.51(s,3H)。 13 C NMR(126MHz,CDCl 3 )δ143.95,127.02,126.76,125.68,125.66,125.45,123.29,15.15。
Example 13
1.0 equivalent of benzothiazole methyl sulfide (0.2 mmol,36.2 mg), 1.0 equivalent of methyl 4-bromobenzoate (0.2 mmol,42.8 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated over anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a colorless liquid (28.5 mg, 78%) was obtained by rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.93(d,J＝8.5Hz,2H),7.24(d,J＝8.5Hz,2H),3.89(s,3H),2.50(s,3H)。 13 C NMR(126MHz,CDCl 3 )δ166.96,145.53,129.96,126.32,124.99,52.13,14.89。
Example 14
1.0 equivalent of benzothiazole methyl sulfide (0.2 mmol,36.2 mg), 1.0 equivalent of 4-bromobenzonitrile (0.2 mmol,36.2 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated over anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a yellow solid (19.6 mg, 66%) was obtained by passing through a rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.54(d,J＝9Hz,2H),7.27-7.23(m,2H),2.51(s,3H)。 13 C NMR(126MHz,CDCl 3 )δ146.24,132.29,125.59,119.13,107.74,14.78。
Example 15
1.0 equivalent of benzothiazole dimethyl sulfide (0.2 mmol,36.2 mg), 1.0 equivalent of 2-bromonaphthalene (0.2 mmol,41.2 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated over anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a white solid (28.5 mg, 82%) was obtained by passing through a rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.79(d,J＝7.5Hz,1H),7.75-7.73(m,2H),7.61(s,1H),7.48(t,J＝7.0Hz,1H),7.43-7.37(m,2H),2.59(s,3H)。 13 C NMR(126MHz,CDCl 3 )δ136.21,134.01,131.39,128.33,127.87,126.94,126.69,125.78,125.36,123.41,15.91。
Example 16
2.0 equivalents of benzothiazole methyl sulfide (0.4 mmol,72.4 mg), 1.0 equivalents of 1, 4-dibromobenzene (0.2 mmol,47.2 mg), pd (OAc) 2 (0.04 mmol,9.0 mg) and Ni (dppe) Cl 2 (0.04 mmol,21.2 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.04 mmol,22.2 mg), 4.0 equivalents of dipotassium hydrogen phosphate (0.8 mmol,140.0 mg) and 5.0 equivalents of zinc powder (1.0 mmol,65.0 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (4.0 mL was added). After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated through anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a colorless liquid (41.4 mg, 61%) was obtained by rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.20(s,4H),2.47(s,6H)。 13 C NMR(126MHz,CDCl 3 )δ135.28,127.74,16.52。
Example 17
2.0 equivalents of benzothiazole dimethyl sulfide (0.2 mmol,36.2 mg), 1.0 equivalents of 2, 7-dibromo-9-hexyl-9H-carbazole (0.1 mmol,40.9 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated through anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a white solid (22.9 mg, 67%) was obtained by passing through a rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.93(d,J＝8.0Hz,2H),7.28(s,2H),7.17(d,J＝8.0Hz,2H),4.23(t,J＝7.5Hz,2H),2.60(s,6H),1.87-1.81(m,2H),1.39-1.26(m,2H),0.88(t,J＝7.0Hz,3H)。 13 C NMR(126MHz,CDCl 3 )δ141.14,135.45,120.81,120.47,118.87,107.55,43.13,31.68,28.93,27.05,22.69,17.26,14.17。GCMS m/z calcd for C 20 H 25 NS 2 [M] + :343 found 343。
Example 18
2.0 equivalents of benzothiazole dimethyl sulfide (0.2 mmol,36.2 mg), 1.0 equivalents of 2, 7-dibromo-9, 9-dihexyl-9H-fluorene (0.1 mmol,49.2 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated through anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a white solid (55.4 mg, 65%) was obtained by passing through a rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.56(d,J＝5.5Hz,2H),7.22-7.20(m,4H),2.54(s,6H),1.92-1.89(m,4H),1.14-1.10(m,4H),1.05-1.03(m,8H),0.78-0.76(t,J＝7.0Hz,6H),0.64-0.58(m,4H)。 13 C NMR(126MHz,CDCl 3 )δ151.35,138.45,136.83,125.63,121.69,119.90,55.25,40.50,31.60,29.78,23.79,22.72,16.73,14.14。
Example 19
1.0 equivalent of benzothiazole ethyl sulfide (0.2 mmol,39.0 mg), 1.0 equivalent of 1-bromo-4-methoxybenzene (0.2 mmol,37.2 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated over anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a colorless liquid (27.5 mg, 82%) was obtained by rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.35(d,J＝8.5Hz,2H),6.86(d,J＝9.0Hz,2H),3.80(s,3H),2.86-2.81(m,2H),1.26-1.23(m,3H)。 13 C NMR(126MHz,CDCl 3 )δ158.94,133.31,126.56,114.60,55.47,29.96,14.77。
Example 20
1.0 equivalent of benzothiazole isopropyl sulfide (0.2 mmol,42.2 mg), 1.0 equivalent of 1-bromo-4-methoxybenzene (0.2 mmol,37.2 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated through anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a colorless liquid (32.5 mg, 89%) was obtained by rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.40(d,J＝9.0Hz,2H),6.85(d,J＝9.0Hz,2H),3.80(s,3H),3.21-3.16(m,1H),1.24(d,J＝6.5Hz,6H)。 13 C NMR(126MHz,CDCl 3 )δ159.49,135.74,125.46,114.44,55.43,39.69,23.24。
Example 21
1.0 eq 2- ((2-ethylhexyl) thio) benzothiazole (0.2 mmol,55.8 mg), 1.0 eq 1-bromo-4-methoxybenzene (0.2 mmol,37.2 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added.After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated over anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a colorless liquid (31.6 mg, 63%) was obtained by rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.34(d,J＝9.0Hz,2H),6.84(d,J＝9.0Hz,2H),3.79(s,3H),2.82(d,J＝6.0Hz,2H),1.50-1.21(m,9H),0.89-0.83(m,6H)。 13 C NMR(126MHz,CDCl 3 )δ158.66,132.73,127.84,114.59,55.46,40.46,39.08,32.32,28.86,25.51,23.10,14.24,10.84。GCMS m/z calcd for C 15 H 24 OS[M] + :252.15 found 252。
Example 22
1.0 eq 2- ((cyclobutylmethyl) thio) benzothiazole (0.2 mmol,47.1 mg), 1.0 eq 1-bromo-4-methoxybenzene (0.2 mmol,37.2 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated through anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a colorless liquid (36.6 mg, 88%) was obtained by rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.34(d,J＝9.0Hz,2H),6.84(d,J＝9.0Hz,2H),3.79(s,3H),2.89(d,J＝7.5Hz,2H),2.48-2.42(m,1H),2.10-2.04(m,2H),1.86-1.79(m,2H),1.73-1.67(m,2H)。 13 C NMR(126MHz,CDCl 3 )δ158.86,133.30,126.87,114.55,55.44,42.56,35.16,28.03,18.09。
GCMS m/z calcd for C 12 H 16 OS[M] + :208.09 found 208。
Example 23
1.0 eq 2- ((cyclopropylmethyl) thio) benzothiazole (0.2 mmol,44.2 mg), 1.0 eq 1-bromo-4-methoxybenzene (0.2 mmol,37.2 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated through anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a colorless liquid (35.0 mg, 90%) was obtained by rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.39(d,J＝8.5Hz,2H),6.84(d,J＝8.5Hz,2H),3.79(s,3H),2.76(d,J＝7.0Hz,2H),1.03-0.95(m,1H),0.55-0.51(m,2H),0.19-0.16(m,2H)。 13 C NMR(126MHz,CDCl 3 )δ158.98,133.56,127.02,114.56,55.46,41.94,11.19,5.61。
Example 24
1.0 eq 2- ((2- (1H-pyrrol-1-yl) ethyl) thio) benzothiazole (0.2 mmol,52.2 mg), 1.0 eq 1-bromo-4-methoxybenzene (0.2 mmol,37.2 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100 ℃ for 12 hours, adding saturated sodium chloride solution into the reaction system to quench the reaction, and then extracting the organic phase with dichloromethane to obtain three phasesThe organic phase was then dehydrated over anhydrous sodium sulfate, then the organic solvent was removed under reduced pressure, and a colorless liquid (38.2 mg, 82%) was obtained by passing through a rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.38(d,J＝8.5Hz,2H),6.88(d,J＝8.5Hz,2H),6.64(s,2H),6.15(s,2H),4.03(t,J＝7.0Hz,2H),3.82(s,3H),3.15(t,J＝7.5Hz,2H)。 13 C NMR(126MHz,CDCl3)δ159.50,134.06,125.07,120.66,114.92,108.50,55.49,48.99,37.39。GCMS m/z calcd for C 13 H 15 NOS[M] + :233.09 found 233。
Example 25
1.0 eq 2- ((2- (naphthalen-1-yl) ethyl) thio) benzothiazole (0.2 mmol,64.1 mg), 1.0 eq 1-bromo-4-methoxybenzene (0.2 mmol,37.2 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated through anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a colorless liquid (30.1 mg, 51%) was obtained by rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.86-7.83(m,2H),7.74(d,J＝8.0Hz,1H),7.48-7.43(m,4H),7.40(t,J＝7.0Hz,1H),7.32(d,J＝7.0Hz,1H),6.90(d,J＝8.5Hz,2H),3.83(s,3H),3.34-3.31(m,2H),3.19-3.15(m,2H)。 13 C NMR(126MHz,CDCl 3 )δ159.21,136.55,133.73,131.74,128.98,127.32,127.00,126.79,126.55,126.31,126.15,125.66,124.22,123.51,122.20,114.77,55.52,36.77,33.46。GCMS m/z calcd for C 19 H 18 OS[M] + :294.11 found 294。
Example 26
1.0 equivalent of benzothiazole phenyl sulfide (0.2 mmol,48.6 mg), 1.0 equivalent of 1-bromo-4-methoxybenzene (0.2 mmol,37.2 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated through anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a white solid (33.7 mg, 78%) was obtained by passing through a rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.57(t,J＝9.0Hz,1H),7.44-7.41(m,2H),7.33-7.26(m,2H),7.18-7.13(m,2H),7.00-6.89(m,2H),3.83(s,3H)。 13 C NMR(126MHz,CDCl 3 )δ135.54,129.06,128.86,128.29,126.87,125.88,115.12,114.31,55.50。
Example 27
1.0 eq 2- (p-toluenesulphonyl) benzothiazole (0.2 mmol,51.4 mg), 1.0 eq 1-bromo-4-methoxybenzene (0.2 mmol,37.2 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated over anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a yellow liquid (36.8 mg, 80%) was obtained by rapid column chromatography)。 1 H NMR(500MHz,CDCl 3 )δ7.37(d,J＝9.0Hz,2H),7.14(d,J＝8.5Hz,2H),7.08(d,J＝8.0Hz,2H),6.88(d,J＝9.0Hz,2H),3.81(s,3H),2.30(s,3H)。 13 C NMR(126MHz,CDCl 3 )δ159.56,136.25,134.50,132.09,129.90,129.47,125.71,114.98,55.49,21.13。
Example 28
1.0 eq 2-methylthiothiazole (0.2 mmol,26.2 mg), 1.0 eq 1-bromo-4-methoxybenzene (0.2 mmol,37.2 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated through anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a colorless liquid (21.9 mg, 71%) was obtained by rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.27(d,J＝9.0Hz,2H),6.85(d,J＝9.0Hz,2H),3.78(s,3H),2.44(s,3H)。 13 C NMR(126MHz,CDCl 3 )δ158.30,130.30,128.86,114.72,55.50,18.22。
Example 29
1.0 equivalent of 4-hexyl-2-phenyl thioether thiophene (0.2 mmol,55.2 mg), 1.0 equivalent of 1-bromo-4-methoxybenzene (0.2 mmol,37.2 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed into the reactionIn a bottle. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated through anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a colorless liquid (33.7 mg, 78%) was obtained by rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.57(t,J＝9.0Hz,1H),7.44-7.41(m,2H),7.33-7.26(m,2H),7.18-7.13(m,2H),7.00-6.89(m,2H),3.83(s,3H)。 13 C NMR(126MHz,CDCl 3 )δ135.54,129.06,128.86,128.29,126.87,125.88,115.12,114.31,55.50。
Example 30
1.0 equivalent of dimethyl disulfide (0.2 mmol,18.8 mg), 1.0 equivalent of 1-bromo-4-methoxybenzene (0.2 mmol,37.2 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated through anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a colorless liquid (24.6 mg, 80%) was obtained by rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.27(d,J＝9.0Hz,2H),6.85(d,J＝9.0Hz,2H),3.78(s,3H),2.44(s,3H)。 13 C NMR(126MHz,CDCl 3 )δ158.30,130.30,128.86,114.72,55.50,18.22。
Example 31
1.0 equivalent of diphenyl disulfide(0.2 mmol,43.6 mg), 1.0 eq 1-bromo-4-methoxybenzene (0.2 mmol,37.2 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated through anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a white solid (33.7 mg, 78%) was obtained by passing through a rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.57(t,J＝9.0Hz,1H),7.44-7.41(m,2H),7.33-7.26(m,2H),7.18-7.13(m,2H),7.00-6.89(m,2H),3.83(s,3H)。 13 C NMR(126MHz,CDCl 3 )δ135.54,129.06,128.86,128.29,126.87,125.88,115.12,114.31,55.50。
Example 32
1.0 equivalent of diethyl disulfide (0.2 mmol,24.4 mg), 1.0 equivalent of 1-bromo-4-methoxybenzene (0.2 mmol,37.2 mg), pd (OAc) 2 (0.02 mmol,4.49 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated over anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a colorless liquid (27.5 mg, 82%) was obtained by rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.35(d,J＝8.5Hz,2H),6.86(d,J＝9.0Hz,2H),3.80(s,3H),2.86-2.81(m,2H),1.26-1.23(m,3H)。 13 C NMR(126MHz,CDCl 3 )δ158.94,133.31,126.56,114.60,55.47,29.96,14.77。
Example 33 (New Synthesis of drug)
1.0 eq benzothiazole methyl sulfide (0.2 mmol,36.2 mg), 1.0 eq 2-bromo-10- (2- (1-methylpiperidin-2-yl) ethyl) -10H-phenothiazine (0.2 mmol,80.8 mg), pd (OAc) 2 (0.02 mmol,4.5 mg) and Ni (dppe) Cl 2 (0.02 mmol,10.6 mg), 1-1' -bis (diphenylphosphorus) ferrocene (0.02 mmol,11.1 mg), 2.0 equivalents of dipotassium hydrogen phosphate (0.4 mmol,69.7 mg) and 2.5 equivalents of zinc powder (0.5 mmol,32.5 mg) were placed in a reaction flask. After three nitrogen substitutions, dry dimethylacetamide (2.0 mL) was added. After stirring at 100℃for 12 hours, a saturated sodium chloride solution was added to the reaction system to quench the reaction, then the organic phase was extracted three times with methylene chloride, the organic phase was dehydrated through anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and a colorless liquid (52.0 mg, 70%) was obtained by rapid column chromatography. 1 H NMR(500MHz,CDCl 3 )δ7.17-7.13(m,2H),7.06(d,J＝8.0Hz,1H),6.93-6.87(m,2H),6.83(d,J＝8.0Hz,1H),6.80(s,1H),3.97-3.81(m,2H),2.47(s,3H),2.22(s,3H),2.13-1.25(m,11H)。 13 C NMR(126MHz,CDCl 3 )δ145.90,145.13,137.66,127.71,127.62,127.37,125.46,122.72,122.40,120.91,115.85,114.73,62.32,57.10,44.07,43.30,31.03,30.14,25.84,24.31,16.63。
Application: synthesis of organic semiconductor Material (5 a,5 b)
The synthesis of 5,5' -dibromo-3, 3' -bis (methylthio) -2,2' -bithiophene comprises the following steps:
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3,3' -Di under nitrogen(methylthio) -2,2' -bithiophene (531.1 mg,2.1 mmol), DCM (5.0 mL) and AcOH (5.0 mL) were added to the reaction tube. The reaction tube was placed in an ice-water bath, and then NBS (806.7 mg,4.5 mmol) was added. The ice-water bath was removed and the mixture was stirred at 25 ℃ for 3 hours. After the reaction was completed. The reaction was treated with 2.0M Na 2 CO 3 The solution (10.0 mL) was quenched and the organic layer extracted with DCM (3X 10.0 mL). The combined organic layers were purified by Na 2 SO 4 The pad was then freed of all volatiles under reduced pressure. The residue was purified by flash column chromatography on silica gel to give the product (835.4 mg, 98%) as a white powder. 1 H NMR(500MHz,CDCl 3 )δ7.02(s,2H),2.41(s,6H)。 13 C NMR(126MHz,CDCl 3 )δ134.14,131.81,131.23,113.62,18.95。GCMS m/z calcd for C 10 H 8 Br 2 S 4 [M] + :416 found 416。
The synthesis of (5 '-hexyl- [2,2' -bithiophene ] -5-yl) trimethylstannane comprises the following steps:
5-hexyl-2, 2' -bithiophene (1000.0 mg,4.0 mmol) was added to a dry reaction tube (100 mL) equipped with a stirring magnet under nitrogen, anhydrous THF (30.0 mL) was added to the reaction tube, and the mixture was stirred at 0deg.C for 3 min. n-BuLi (1.8 mL,2.5M in hexane) was slowly added to the reaction solution at 0deg.C, and the mixture was stirred at 0deg.C for 2 hours. Me is added to the mixture at 0 DEG C 3 SnCl (4.4 mL,1.0M in hexane) and then the reaction tube was slowly warmed to room temperature and stirred at 25℃for 12 hours. After completion of the reaction, the reaction was quenched with 2.0M NaCl solution (10.0 mL) and the organic layer was extracted with DCM (3X 50.0 mL). The combined organic layers were purified by Na 2 SO 4 Pad, then all volatiles were removed under reduced pressure to give the product (1650.0 mg) as a green liquid which was used directly in the next step without purification. 1 H NMR(500MHz,CDCl 3 )δ7.22(d,J＝3.5Hz,1H),7.08(d,J＝3.5Hz,1H),6.98(d,J＝3.5Hz,1H),6.68(d,J＝3.5Hz,1H),3.77(t,J＝6.5Hz,2H),2.80(t,J＝7.5Hz,2H),1.87-1.85(m,2H),1.71-1.65(m,4H),0.92(t,J＝7.0Hz,3H),0.44-0.33(m,9H)。
The synthesis of 4-hexyl-2-trimethylstannane-4H-dithieno [3,2-b:2',3' -d ] pyrrole comprises the following steps:
a dry reaction tube (100 mL) equipped with a stirring magnet was charged under nitrogen with 4-hexyl-4H-dithieno [3,2-b:2',3' -d ]]Pyrrole (1052.0 mg,4.0 mmol) dry THF (30.0 mL) was added to the reaction tube and the mixture was stirred at 0deg.C for 3 min. n-BuLi (1.8 mL,2.5M in hexane) was slowly added to the reaction solution at 0deg.C, and the mixture was stirred at 0deg.C for 2 hours. Me is added to the mixture at 0 DEG C 3 SnCl (4.4 mL,1.0M in hexane) and then the reaction tube was slowly warmed to room temperature and stirred at 25℃for 12 hours. After the reaction was completed, the reaction was quenched with 2.0M NaCl solution (10.0 mL). The organic layer was extracted with DCM (3X 50.0 mL). The combined organic layers were purified by Na 2 SO 4 The pad was then freed of all volatiles under reduced pressure to give the product (1701.0 mg) as a green liquid which was used directly in the next step without purification. 1 H NMR(500MHz,CDCl 3 )δ7.15-7.11(m,1H),7.07-7.00(m,2H),4.22(t,J＝7.0z,2H),1.93-1.87(m,2H),1.39-1.31(m,6H),0.92(t,J＝5.5Hz,3H).0.51-0.40(m,9H)。
5a synthesis step:
5,5' -dibromo-3, 3' -bis (methylthio) -2,2' -bithiophene (831.6 mg,2.0 mmol) was reacted under nitrogen with (5 ' -hexyl- [2,2' -bithiophene)]5-yl) trimethylstannane (1650.0 mg) and tetrakis triphenylphosphine palladium (231.1 mg,0.2 mmol) were added to the reaction tube, and the mixture was dissolved in anhydrous toluene (10.0 mL), and the reaction system was stirred at 100℃for 12 hours. After the reaction was completed, the reaction tube was cooled to room temperature. The reaction was quenched with 2.0M NaCl solution (10.0 mL). D for organic layerCM (3X 50.0 mL) extraction. The combined organic layers were purified by Na 2 SO 4 The pad was then freed of all volatiles under reduced pressure. The residue was purified by flash column chromatography on silica gel to give the product (1360.0 mg, 90%) as a red powder. 1 H NMR(500MHz,CDCl 3 )δ7.11(s,2H),7.09(d,J＝4.0Hz,2H),7.01-6.99(m,4H),6.70(d,J＝3.5Hz,2H),2.81(s,4H),2.49(s,6H),1.71-1.65(m,4H),1.43-1.27(m,12H),0.91(t,J＝7.0Hz,6H)。 13 C NMR(126MHz,CDCl 3 )δ145.99,137.67,137.40,134.41,133.96,129.03,125.37,125.00,124.87,123.67,31.69,30.32,28.89,22.71,19.04,14.24。MS(MALDI)m/z calcd for C 38 H 42 S 8 [M] + :754.11 found 754。
5b synthesis step:
5,5' -dibromo-3, 3' -bis (methylthio) -2,2' -bithiophene (831.6 mg,2.0 mmol), 4-hexyl-2- (trimethylstannyl) -4H-dithieno [3,2-b:2',3' -d]Pyrrole (1710.0 mg) and tetraphenylphosphine palladium (231.1 mg,0.2 mmol) were added to the reaction tube, and the mixture was dissolved in anhydrous toluene (10.0 mL), and the reaction system was stirred at 100℃for 12 hours. After the reaction was completed, the reaction tube was cooled to room temperature. The reaction was quenched with 2.0M NaCl solution (10.0 mL) and the organic layer extracted with DCM (3X 50.0 mL). The combined organic layers were purified by Na 2 SO 4 The pad was then freed of all volatiles under reduced pressure. The residue was purified by flash column chromatography on silica gel to give the product (1200.0 mg, 74%) as a red powder. 1 H NMR(500MHz,CDCl 3 )δ7.17(d,J＝5.5Hz,2H),7.16(s,2H),7.14(s,2H),7.00(d,J＝5.0Hz,2H),4.20(t,J＝7.0Hz,4H),2.52(s,6H),1.91-1.85(m,4H),1.37-1.25(m,12H),0.89(t,J＝7.0Hz,6H)。 13 C NMR(126MHz,CDCl 3 )δ145.34,144.78,139.08,133.83,133.44,128.73,124.87,123.93,115.00,114.53,111.05,108.10,47.62,31.58,30.50,26.82,22.68,19.15,14.18。MS(MALDI)m/z calcd for C 38 H 40 N 2 S 8 [M] + :780.10 found 780。
TABLE 1 absorption maxima and energy level levels for organic semiconductor materials
a Measurement in chloroform 10 -6 The solution of M was absorbed and the film was drop cast from the chloroform solution onto a quartz substrate. b On CH 2 Cl 2 /0.1M[ n Bu 4 N] + [PF 6 ] – In relation to 50 mV/s. c E g opt Is the optical bandgap estimated from the initial absorption edge of the film. d From the LUMO estimated from the reduction potential, it is assumed that the absolute energy level of ferrocene under vacuum is 4.8eV; e HOMO＝LUMO-E g opt 。
as shown in fig. 1,2 and table 1, 5a showed good thermal stability with a decomposition temperature of about 443 ℃. The compound has no visible thermal transition up to 400 ℃.5b shows good thermal stability and a decomposition temperature of about 361 ℃. The compound has no visible thermal transition up to 320 ℃.
Although embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that: various substitutions, changes and modifications are possible without departing from the spirit and scope of the invention and the appended claims, and therefore the scope of the invention is not limited to the disclosure of the embodiments.

Claims (3)

1. A method for synthesizing aromatic thioether through aromatic exchange bimetallic catalysis is characterized in that: the reaction formula is shown as follows:
the saidIs any one of the following compounds:
wherein LG is Br, I, cl;
wherein R, R 1 ,R 2 Is independent C 1 -C 15 Is a chain alkyl group; the saidIs any one of the following compounds:
2. the method for synthesizing aromatic thioether through the catalysis of the aromatic exchange bimetallic according to claim 1, wherein: the method comprises the following specific steps:
(1) In Pd (OAc) under inert gas protection 2 ，Ni(dppe)Cl 2 Adding dppf and dipotassium hydrogen phosphate as additives, activated Zn powder as reducing agent, and dryingMolecular sieve, thioether acceptor aryl electrophile +.>With aryl sulfide source->Placing in dimethylacetamide to make reverse reactionA mixture should be obtained;
(2) Dropping saturated sodium chloride solution into the mixture to quench, extracting with dichloromethane for three times, removing water from the organic phase through anhydrous sodium sulfate, removing the organic solvent under reduced pressure, and purifying by a rapid column chromatography to obtain the product.
3. The method for synthesizing aromatic thioether through the catalysis of the aromatic exchange bimetallic according to claim 1, wherein: the specific synthesis method comprises the following steps:
1.0 equivalent of an aryl sulfide source1.0 equivalent of aryl electrophile +.>10.0mol% Pd (OAc) 2 10.0mol% Ni (dppe) Cl 2 10.0mol% of 1-1' -bis (diphenylphosphorus) ferrocene, 2.0 equivalents of dipotassium hydrogen phosphate and 2.5 equivalents of zinc powder were placed in a reaction flask; after three nitrogen substitutions, dry dimethylacetamide was added to maintain the concentration of the solution at 0.1M, dry +.>A molecular sieve; stirring at 100deg.C for 12 hr, adding saturated sodium chloride solution into the reaction system, quenching, extracting the organic phase with dichloromethane for three times, removing water from the organic phase with anhydrous sodium sulfate, removing the organic solvent under reduced pressure, and passing through quick column chromatography to obtain the final product.
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