WO2022178736A1 - Procédé de préparation d'un composé de biphényl benzothiazole - Google Patents

Procédé de préparation d'un composé de biphényl benzothiazole Download PDF

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Publication number
WO2022178736A1
WO2022178736A1 PCT/CN2021/077750 CN2021077750W WO2022178736A1 WO 2022178736 A1 WO2022178736 A1 WO 2022178736A1 CN 2021077750 W CN2021077750 W CN 2021077750W WO 2022178736 A1 WO2022178736 A1 WO 2022178736A1
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Prior art keywords
biphenyl
benzothiazole compound
preparing
reaction
compound according
Prior art date
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PCT/CN2021/077750
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English (en)
Chinese (zh)
Inventor
李红喜
王昊
李海燕
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苏州大学
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Publication date
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Priority to PCT/CN2021/077750 priority Critical patent/WO2022178736A1/fr
Publication of WO2022178736A1 publication Critical patent/WO2022178736A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
    • C07D277/66—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2 with aromatic rings or ring systems directly attached in position 2

Definitions

  • the invention belongs to the technical field of organic chemical synthesis methodology, in particular to a preparation method of a biphenyl benzothiazole compound.
  • Biphenylbenzothiazole compounds can be prepared from 2-substituted benzothiazoles.
  • 2-Substituted benzothiazole compounds are prepared under visible or ultraviolet light irradiation under the catalysis of transition metal complexes such as [Ru(bpy) 3 ] 2+ , [Ir(ppy) 3 ] or organic photosensitizers , these reactions often add additional equipment, reagents, or separation costs, and may introduce toxic heavy metals or organic pollutants.
  • the present invention discloses a brand-new visible light-promoted one-pot method for preparing biphenyl benzothiazole compounds from N-(2-bromophenyl) thioamides.
  • the present invention adopts the following technical scheme: a preparation method of a biphenyl benzothiazole compound, comprising the following steps, under visible light irradiation, in the presence of a base, with N-(2-bromophenyl) thioamide Intramolecular cross-coupling reaction is carried out as raw materials to prepare benzothiazole compounds; then benzothiazole compounds and phenylboronic acid are used as raw materials to catalyze the reaction to prepare biphenyl benzothiazole compounds.
  • the invention adopts a one-pot method to prepare the biphenyl benzothiazole compound. After the intramolecular cross-coupling reaction is completed, phenylboronic acid, a catalyst and potassium carbonate are directly added, and the biphenyl benzothiazole compound is obtained by heating for catalytic reaction.
  • the intramolecular cross-coupling reaction is carried out at room temperature for 2-5 hours; the intramolecular cross-coupling reaction is carried out in a solvent under the protection of an inert gas.
  • the molar ratio of N-(2-bromophenyl)thioamide and base is 1:(0.2-0.8), preferably 1:0.2-0.5, and most preferably 1:0.5.
  • N-(2-bromophenyl) thioamide and benzothiazole compounds respectively have the following general structural formula: .
  • R4 is selected from fluorine, chlorine, bromine, iodine, methyl, methoxy, tert - butyl or trifluoromethyl.
  • the catalytic reaction is carried out in the presence of a palladium catalyst, potassium carbonate, a solvent, and an inert gas.
  • the temperature of the catalytic reaction is 100-120° C., and the time is 3-6 hours.
  • the inert gas is selected from any one of nitrogen, helium, neon, and argon, preferably nitrogen;
  • the base is any one of inorganic bases, and the inorganic base is selected from sodium phosphate, sodium carbonate , any one of potassium carbonate, potassium hydroxide, sodium hydroxide, and sodium acetate, preferably sodium phosphate;
  • the solvent is dimethyl sulfoxide (DMSO), DMF, tetrahydrofuran (THF), methanol, ethanol, acetonitrile (MeCN), etc. .
  • the reaction for preparing the benzothiazole compounds in the invention is carried out without photosensitizer or transition metal catalyst, which effectively solves the problem of the need for auxiliary (transition) catalyst in the prior art; the reaction can occur immediately after irradiation by a simple 45W household compact fluorescent lamp , and achieved unexpected technical results. Further, the biphenyl benzothiazole compound is effectively prepared by using the benzothiazole compound, and the whole process is green, efficient and easy to operate, which is a good method for synthesizing the benzothiazole compound.
  • the present invention can obtain benzothiazole compounds simply and efficiently without other reagents and reaction steps.
  • the stirring device is a magnetic stirring device; the reaction vessel is a sealed reaction tube.
  • the bromine site in the N-(2-bromophenyl)thioamide reacts with the sulfur site to prepare benzothiazole compounds, and the reaction is clear.
  • the present invention will be further described below with reference to specific embodiments. Unless otherwise specified, the reagents, materials, instruments, etc. used in the following examples are all commercially available.
  • the reaction of obtaining benzothiazole compounds in the present invention is carried out in the absence of photosensitizer or transition metal catalyst, and only N-(2-bromophenyl) thioamide, inorganic base and DMSO are used as raw materials; the reaction in the embodiment of the present invention Performed at room temperature, using a 45W domestic compact fluorescent lamp as the visible light source.
  • the specific experiments and testing methods of the present invention are conventional techniques.
  • Example 1 Visible light promotes the reaction of N-(2-bromophenyl)thiobenzamide.
  • Example 2 Visible light promotes the reaction of N-(2-bromophenyl)-4-chlorothiobenzamide.
  • N-(2-Bromophenyl)-4 - chlorothiobenzamide (0.2 mmol), Na3PO4 (0.1 mmol), and DMSO ( 2 mL) were added to a dry reaction tube with a magnetic stir bar Then, the reaction tube was replaced with N 3 times, and the reaction was stirred for 5 h under the irradiation of a 45W household compact fluorescent lamp. After the reaction, 4 mL of water was added, then extracted with 3 ⁇ 4 mL of ethyl acetate, the organic phases were combined, the organic phases were dried over anhydrous sodium sulfate, filtered, the filtrate was concentrated by rotary evaporation, and separated by thin-layer chromatography on silica gel. , the target product was obtained with a yield of 93%.
  • Example 3 Visible light promotes the reaction of N-(2-bromophenyl)-4-bromothiobenzamide.
  • N-(2-Bromophenyl)-4 - bromothiobenzamide (0.2 mmol), Na3PO4 (0.1 mmol), and DMSO ( 2 mL) were added to a dry reaction tube with a magnetic stir bar Then, the reaction tube was replaced with N 3 times, and the reaction was stirred for 5 h under the irradiation of a 45W household compact fluorescent lamp. After the reaction, 4 mL of water was added, then extracted with 3 ⁇ 4 mL of ethyl acetate, the organic phases were combined, the organic phases were dried over anhydrous sodium sulfate, filtered, the filtrate was concentrated by rotary evaporation, and separated by thin-layer chromatography on silica gel. , the target product was obtained with a yield of 91%.
  • Example 4 Visible light promotes the reaction of N-(2-bromophenyl)-4-iodothiobenzamide.
  • N-(2-Bromophenyl)-4- iodothiobenzamide (0.2 mmol), Na3PO4 (0.1 mmol), and DMSO ( 2 mL) were added to a dry reaction tube with a magnetic stir bar Then, the reaction tube was replaced with N 3 times, and the reaction was stirred for 5 h under the irradiation of a 45W household compact fluorescent lamp. After the reaction, 4 mL of water was added, then extracted with 3 ⁇ 4 mL of ethyl acetate, the organic phases were combined, the organic phases were dried over anhydrous sodium sulfate, filtered, the filtrate was concentrated by rotary evaporation, and separated by thin-layer chromatography on silica gel. , the target product was obtained with a yield of 86%.
  • the DMSO was replaced with a mixed solution of 1 mL of THF and 1 mL of acetonitrile, and the rest remained unchanged, and the product yield was 39%.
  • Example 5 Visible light promoted N-(2-bromophenyl)-4-trifluoromethylthiobenzamide reaction.
  • N-(2-Bromophenyl)-4 - trifluoromethylthiobenzamide (0.2 mmol), Na3PO4 (0.1 mmol), and DMSO ( 2 mL) were added to dry with a magnetic stir bar Then, the reaction tube was replaced with N 3 times, and the reaction was stirred for 24 h under the irradiation of a 45W household compact fluorescent lamp. After the reaction, 4 mL of water was added, then extracted with 3 ⁇ 4 mL of ethyl acetate, the organic phases were combined, the organic phases were dried over anhydrous sodium sulfate, filtered, the filtrate was concentrated by rotary evaporation, and separated by thin-layer chromatography on silica gel. , the target product was obtained with a yield of 94%.
  • N-(2-Bromophenyl)-4-iodothiobenzamide (58.4 mg, 0.2 mmol, 1.0 equiv), Na3PO4 ( 0.1 mmol), and DMSO ( 2 mL) were added with magnetic stirring In a dry reaction tube, the reaction tube was then replaced with N 3 times, and the reaction was stirred for 5 h under the irradiation of a 45W household compact fluorescent lamp.
  • the reaction mixture was cooled to room temperature, 4 mL of water was added, then extracted with 3 ⁇ 4 mL of ethyl acetate, the organic phases were combined, the organic phases were dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation, Separation by thin-layer chromatography on silica gel gave the target product biphenylbenzothiazole compound, 48.5 mg of white solid.
  • the DMSO was replaced with a mixed solution of 1 mL of THF and 1 mL of methanol, and the rest remained unchanged, and no white product biphenylbenzothiazole compound was obtained.
  • the whole reaction process of the invention is green, efficient and easy to operate, and is a good method for synthesizing benzothiazole compounds, and further, the biphenyl benzothiazole compound can be obtained by reacting with phenylboronic acid.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de préparation d'un composé de biphényl benzothiazole. Selon la présente invention, un composé de biphényl benzothiazole est préparé à l'aide de N-(2-bromophényle)alkylthioamides tels qu'un dérivé de N-(2-bromophényle)alkylthioamide en tant que matières premières, en utilisant du phosphate de sodium en tant qu'alcali et au moyen d'un procédé monotope. La réaction dans la présente invention est réalisée sous irradiation de lumière visible sans ions métalliques décrits dans l'état de la technique, et a un rendement de réaction élevé.
PCT/CN2021/077750 2021-02-24 2021-02-24 Procédé de préparation d'un composé de biphényl benzothiazole WO2022178736A1 (fr)

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PCT/CN2021/077750 WO2022178736A1 (fr) 2021-02-24 2021-02-24 Procédé de préparation d'un composé de biphényl benzothiazole

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102153593A (zh) * 2011-02-21 2011-08-17 四川大学 红光有机电致磷光铱配合物
CN112939891A (zh) * 2021-02-23 2021-06-11 苏州大学 一种制备联苯苯并噻唑化合物的方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102153593A (zh) * 2011-02-21 2011-08-17 四川大学 红光有机电致磷光铱配合物
CN112939891A (zh) * 2021-02-23 2021-06-11 苏州大学 一种制备联苯苯并噻唑化合物的方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BOWMAN W.RUSSELL, HEANEY HARRY, SMITH PHILIP H.G.: "Intramolecular aromatic substitution (SRN1) reactions; use of entrainment for the preparation of benzothiazoles", TETRAHEDRON LETTERS, ELSEVIER, AMSTERDAM , NL, vol. 23, no. 48, 1 January 1982 (1982-01-01), Amsterdam , NL , pages 5093 - 5096, XP055961522, ISSN: 0040-4039, DOI: 10.1016/S0040-4039(00)85581-1 *
DHAYALAN VASUDEVAN, HAYASHI MASAHIKO: "Synthesis of 2-Arylbenzothiazole Derivatives Based on Activated Carbon/Oxygen Oxidation Followed by Suzuki-Miyaura Coupling", SYNTHESIS, GEORG THIEME VERLAG, STUTTGART, DE., vol. 44, no. 14, 1 July 2012 (2012-07-01), STUTTGART, DE. , pages 2209 - 2216, XP055961524, ISSN: 0039-7881, DOI: 10.1055/s-0031-1289772 *

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