CN115010563B - Method for preparing different halogenated aromatic hydrocarbons by visible light promoted nickel-catalyzed halogen exchange - Google Patents

Method for preparing different halogenated aromatic hydrocarbons by visible light promoted nickel-catalyzed halogen exchange Download PDF

Info

Publication number
CN115010563B
CN115010563B CN202210798650.XA CN202210798650A CN115010563B CN 115010563 B CN115010563 B CN 115010563B CN 202210798650 A CN202210798650 A CN 202210798650A CN 115010563 B CN115010563 B CN 115010563B
Authority
CN
China
Prior art keywords
reaction
nickel
room temperature
added
visible light
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210798650.XA
Other languages
Chinese (zh)
Other versions
CN115010563A (en
Inventor
林禄清
冯云会
罗杭
郑婉瑶
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian University of Technology
Original Assignee
Dalian University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian University of Technology filed Critical Dalian University of Technology
Priority to CN202210798650.XA priority Critical patent/CN115010563B/en
Publication of CN115010563A publication Critical patent/CN115010563A/en
Application granted granted Critical
Publication of CN115010563B publication Critical patent/CN115010563B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B39/00—Halogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/208—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being MX
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention relates to a method for efficiently preparing aryl halide, which realizes halogen exchange reaction of the aryl halide under the irradiation of visible light, and obtains target aryl halide by taking a compound formed endogenously by nickel and a bipyridyl ligand as a catalyst. The method avoids the use of a toxic solvent with high boiling point and large polarity, has mild reaction conditions, can obtain different types of aryl halides with high yield at room temperature and lower catalyst consumption, and is a novel method which has high efficiency, good operability and environmental friendliness and is suitable for industrial production.

Description

Method for preparing different halogenated aromatic hydrocarbons by visible light promoted nickel-catalyzed halogen exchange
Technical Field
The invention belongs to the technical field of chemical industry, and relates to a method for preparing different halogenated aromatic hydrocarbons by visible light-promoted nickel-catalyzed halogen exchange of aryl halides.
Background
Aryl halides are media of different organic reactions, and are widely applied to various transition metal catalyzed cross-coupling reactions, pesticides and other chemicals. In common chemical reactions, on the one hand, aryl iodide compounds tend to be more active than aryl bromides and aryl chlorides; on the other hand, due to the inertness of the aryl bromide and the aryl chloride, the occurrence of unnecessary reactions can be prevented in the chemical system. It is therefore necessary to achieve interconversion between the halogen atoms of the aryl halides. Through research on documents, the method finds that copper and nickel are firstly used for halogen exchange reaction of aryl halides, and still has some defects and shortcomings, the reaction conditions are harsh, the reaction temperature is high, the boiling point of a solvent is high, the polarity is high, a calculated amount of metal needs to be added to promote the reaction, the environment friendliness is poor, the conversion rate is low, and the separation and purification of products are not facilitated. The invention is a new method for preparing aryl halide by nickel catalysis, different aryl halides are synthesized by promoting the exchange of aryl halide halogen catalyzed by nickel through visible light, the method has the characteristics of high conversion rate, very mild conditions and the like, and the method is a safe and practical new method for preparing aryl halide in a green and high-efficiency manner.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for preparing different halogenated aromatic hydrocarbons by visible light-induced nickel-catalyzed halogen exchange of aryl halides.
The technical scheme adopted by the invention is as follows:
a method for preparing different halogenated aromatic hydrocarbons by visible light promoted nickel catalyzed halogen exchange is characterized in that under the protection of nitrogen, a nickel source is added into a reaction solvent, bipyridyl is stirred for 10 minutes at room temperature, then aryl halide and sodium iodide (tetrabutylammonium bromide/triethylbenzylammonium chloride) are added, and the mixture is stirred and irradiated by light at a proper temperature for 12-48 hours to obtain a halogen exchanged product. The specific reaction process is as follows:
Figure SMS_1
wherein, X1 is bromine or chlorine; x 2 Is iodine or bromine; r 1 Is a single substituent or a polysubstituent on a benzene ring; YX 2 Is an iodine source or a bromine source; ZX 1 Is a source of bromide or chloride ions.
During the reaction, the reaction temperature is 25-70 ℃, and the molar ratio of the substrate aryl halide to the catalyst is 10:1-20:1, the molar ratio of substrate aryl halide to ligand is 25:3-50:3, the concentration of the substrate is 0.1M, the concentration of the metal salt is 0.2-0.6M, and the halogen exchange reaction time is 12-48h.
Further characterized in that the LED blue light lamp (with the wavelength range of 410-480 nm) is used as a visible light source.
Further characterized, the aryl halide may contain various substituents such as methyl, t-butyl, methoxy, amine, trifluoromethyl, trifluoromethoxy, aldehyde, acetyl, cyano, phenyl, ester, and the like.
Further characterized in that said nickel source comprises zero-valent nickel and divalent nickel and their related nickel complexes; the nickel source is preferably bis (1, 5-cyclooctadiene) nickel, and the nickel complex refers to Ni (cod) 2 、NiCl 2 、NiBr 2 、NiI 2 Or Ni (OAc) 2 。
Further characterized in that the bipyridyl ligand is 4, 4-di-tert-butyl bipyridyl, 4-di-methyl bipyridyl, 4-di-methoxy bipyridyl or 2, 2-bipyridyl, and preferably 4, 4-di-tert-butyl-2, 2-bipyridyl.
The bromine source is tetrabutylammonium bromide;
the chlorine source is triethyl benzyl ammonium chloride.
Further characterized in that the iodide ion is sodium iodide or potassium iodide;
further characterized in that the solvent is an ether solvent which is 1,4-dioxane tetrahydrofuran, cyclopentyl methyl ether, 2-methyl tetrahydrofuran or 1,4-dioxane, preferably 1,4-dioxane and cyclopentyl methyl ether.
In the method, salt with poorer dissolubility is precipitated in the positive direction of the reversible reaction, so that the reaction is promoted to be carried out in the positive direction; the reverse direction of the reversible reaction generates a more stable C-X bond, thereby facilitating the reaction to proceed in the reverse direction. The solvents used are slightly less polar, have a low boiling point and are less toxic (1, 4-dioxane or cyclopentyl methyl ether). Can obtain higher conversion rate under the condition of lower catalyst dosage, and has mild reaction condition and simple and safe operation.
Detailed Description
The invention is further illustrated by the following examples, the following examples being only for the understanding of the invention and not to limit the content thereof.
In the following examples, according to R 1 The substituents are different and 1a, 1b, 1c, 1d, 1e, 1f, 1g, 1h, 1i, 1j, 1k,3a, 3b, 3c, 3d, 3e, 3f, 3g, 3h, 3i, 3j, 3k represent various aryl bromides and aryl chlorides represented by the general formula (1). 2a, 2b, 2c, 2d, 2e, 2f, 2g, 2h, 2i, 2j, 2k represent various different channelsAn aryl iodide represented by the formula (2).
Example 1:
2a(X 2 ＝I,R 1 preparation of = 4-Ph)
Weighing dry catalyst Ni (COD) in glove box 2 (2.8mg, 0.01mmol,5 mol%) and dtbbpy (3.2mg, 0.012mmol,6 mol%) were charged to a 10ml dry clean schlenk tube equipped with a stirrer, and CPME (1 ml) was added and stirred at room temperature for 10 minutes. Sodium iodide (60mg, 0.4 mmol), corresponding to 1a (X), was weighed out 1 ＝Br,R 1 = 4-Ph) (46.4mg, 0.2mmol), followed by addition of 1ml of CPME, sealing and reaction at 50 ℃ for 12 hours under 455nm blue light irradiation, yield 99%.2a: 1 H NMR(400MHz,CDCl 3 ):δ7.79-7.77 (m,2H),7.59-7.55(m,2H),7.49-7.43(m,2H),7.40-7.33(m,3H)。
example 2:
2b(X 2 ＝I,R 1 = 4-CHO) preparation
Weighing dry catalyst Ni (COD) in glove box 2 (2.8mg, 0.01mmol,5 mol%) and dtbbpy (3.2mg, 0.012mmol,6 mol%) were put into a 10ml dry clean schlenk tube equipped with a stirrer, and CPME (1 ml) was added and stirred at room temperature for 10 minutes. Sodium iodide (60mg, 0.4 mmol), corresponding to 1b (X), was weighed out 1 ＝Br,R 1 = 4-CHO) (34.2mg, 0.2mmol), followed by addition of 1ml of CPME, sealing and reaction at 50 ℃ for 36 h under 455nm blue light irradiation, 83% yield. 2b: 1 H NMR(400MHz,CDCl 3 ):δ9.96 (s,1H),7.92-7.90(d,J＝8.2Hz,2H),7.60-7.58(d,J＝8.2Hz,2H)。
example 3:
2c(X 2 ＝I,R 1 preparation of = 4-CN)
Weighing dry catalyst Ni (COD) in glove box 2 (2.8mg, 0.01mmol,5 mol%) and dtbbpy (3.2mg, 0.012mmol,6 mol%) were put into a 10ml dry clean schlenk tube equipped with a stirrer, and CPME (1 ml) was added and stirred at room temperature for 10 minutes. Sodium iodide (60mg, 0.4 mmol), corresponding 1c (X) was weighed out 1 ＝Br,R 1 = 4-CN) (36.4mg, 0.2mmol), and then 1ml of CPME was added, and after sealing, reaction was carried out at 50 ℃ for 36 hours under blue light irradiation at 455nm, with a yield of 99%.2c: 1 H NMR(400MHz,CDCl 3 ):δ7.85(d, J＝7.9Hz,2H),7.37(d,J＝8.2Hz,2H)。
example 4:
2d(X 2 ＝I,R 1 ＝4- t bu) preparation
Weighing dry catalyst Ni (COD) in glove box 2 (2.8mg, 0.01mmol,5 mol%) and dtbbpy (3.2mg, 0.012mmol,6 mol%) were put into a 10ml dry clean schlenk tube equipped with a stirrer, and CPME (1 ml) was added and stirred at room temperature for 10 minutes. Sodium iodide (60mg, 0.4mmol), corresponding to 1d (X), was weighed out 1 ＝Br,R 1 ＝4- t Bu)(42.4mg,0.2mmol)
Then 1ml of CPME is added, and after sealing, the reaction is carried out for 36 hours at 50 ℃ under the irradiation of 455nm blue light, and the yield is 96 percent. 2d: 1 H NMR(400MHz,CDCl 3 ):δ7.62(d,J＝8.6Hz,2H),7.15(d,J＝8.6Hz, 2H),1.30(s,9H)。
example 5:
2e(X 2 ＝I,R 1 preparation of = 4-OMe)
Weighing dry catalyst Ni (COD) in glove box 2 (2.8mg, 0.01mmol,5 mol%) and dtbbpy (3.2mg, 0.012mmol,6 mol%) were put into a 10ml dry clean schlenk tube equipped with a stirrer, and CPME (1 ml) was added and stirred at room temperature for 10 minutes. Sodium iodide (60mg, 0.4 mmol), the corresponding 1e (X) was weighed out 1 ＝Br,R 1 = 4-OMe) (37.4mg, 0.2mmol), and then 1ml of CPME was added, and after sealing, reaction was carried out at 50 ℃ for 36 hours under 455nm blue light irradiation with a yield of 88%.2e: 1 H NMR(400MHz,CDCl 3 ):δ7.56 (d,J＝8.9Hz,2H),6.68(d,J＝8.9Hz,2H),3.78(s,3H)。
example 5:
2f(X 2 ＝I,R 1 preparation of = 3-Me)
Weighing dry catalyst Ni (COD) in glove box 2 (2.8mg, 0.01mmol,5 mol%) and dtbbpy (3.2mg, 0.012mmol,6 mol%) were charged to a 10ml dry clean schlenk tube equipped with a stirrer, and CPME (1 ml) was added and stirred at room temperature for 10 minutes. Sodium iodide (60mg, 0.4 mmol), the corresponding 1f (X) was weighed out 1 ＝Br,R 1 = 3-Me) (34.2mg, 0.2mmol), followed by addition of 1ml of CPME, sealing, and reaction at 50 ℃ for 36 hours under 455nm blue light irradiation, yield 97%。2f: 1 H NMR(400MHz,CDCl 3 ):δ7.56(s, 1H),7.50(d,J＝7.9Hz,1H),7.14(d,J＝7.7Hz,1H),6.99(t,J＝7.7Hz,1H),2.31 (s,3H)。
Example 6:
2g(X 2 ＝I,R 1 preparation of =3,5-Me)
Weighing dry catalyst Ni (COD) in glove box 2 (2.8mg, 0.01mmol,5 mol%) and dtbbpy (3.2mg, 0.012mmol,6 mol%) were put into a 10ml dry clean schlenk tube equipped with a stirrer, and CPME (1 ml) was added and stirred at room temperature for 10 minutes. Sodium iodide (60mg, 0.4 mmol), corresponding to 1g (X), was weighed out 1 ＝Br,R 1 =3,5-Me) (37mg, 0.2mmol), followed by addition of 1ml of CPME, sealing, and reaction at 50 ℃ for 36 hours under 455nm blue light irradiation, yield 78%.2g: 1 H NMR(400MHz,CDCl 3 ):δ7.35(s, 2H),6.95(s,1H),2.27(s,6H)。
example 7:
2h(X 2 ＝I,R 1 preparation of =2,6-Me)
Weighing dry catalyst Ni (COD) in glove box 2 (2.8mg, 0.01mmol,5 mol%) and dtbbpy (3.2mg, 0.012mmol,6 mol%) were put into a 10ml dry clean schlenk tube equipped with a stirrer, and CPME (1 ml) was added and stirred at room temperature for 10 minutes. Sodium iodide (60mg, 0.4 mmol) was weighed in for 1h (X) 1 ＝Br,R 1 =2,6-Me) (37mg, 0.2mmol), followed by addition of 1ml of CPME, sealing, and reaction at 50 ℃ for 36 hours under blue light irradiation at 455nm, yield 96%.2h: 1 H NMR(400MHz,CDCl 3 ):δ7.15-7.10 (m,1H),7.06(d,J＝7.5Hz,2H),2.49(s,6H)。
example 8:
2i(X 2 ＝I,R 1 preparation of = 2-Me)
Weighing dry catalyst Ni (COD) in glove box 2 (2.8mg, 0.01mmol,5 mol%) and dtbbpy (3.2mg, 0.012mmol,6 mol%) were charged to a 10ml dry clean schlenk tube equipped with a stirrer, and CPME (1 ml) was added and stirred at room temperature for 10 minutes. Sodium iodide (60mg, 0.4 mmol), the corresponding 1i (X) was weighed out 1 ＝Br,R 1 = 2-Me) (34.2mg, 0.2mmol), followed by addition of 1ml of CPME, sealing, reaction at 50 ℃ for 36 hours under 455nm blue light irradiation,the yield thereof was found to be 85%.2i: 1 H NMR(400MHz,CDCl 3 ):δ7.81(d, J＝7.9Hz,1H),7.24(d,J＝4.7Hz,2H),6.91-6.83(m,1H),2.44(s,3H)。
example 9:
1a(X 1 ＝Br,R 1 preparation of = 4-Ph)
Weighing dry catalyst Ni (COD) in glove box 2 (5.5mg, 0.02mmol, 10mol%) and dtbbpy (6.4mg, 0.024mmol, 12mol%) were put into a 10ml dry clean schlenk tube equipped with a stirrer, and 1,4-dioxane (1 ml) was added thereto, followed by stirring at room temperature for 10 minutes. Tetrabutylammonium bromide (128.8mg, 0.4mmol), the corresponding 2a (X) was weighed out 2 ＝I,R 1 = 4-Ph) (60mg, 0.2mmol), followed by addition of 1ml of CPME, sealing and reaction at room temperature under blue light irradiation at 455nm for 36 hours, yield 93%.1a: 1 H NMR(400MHz, CDCl 3 ):δ7.59-7.54(m,4H),7.48-7.43(m,4H),7.38(d,J＝7.3Hz,1H)。
example 10:
1b(X 1 ＝Br,R 1 = 4-CHO) preparation
Weighing dry catalyst Ni (COD) in glove box 2 (5.5 mg,0.02mmol, 10mol%) and dtbbpy (6.4 mg,0.024mmol, 12mol%) were put into a 10ml dry and clean schlenk tube equipped with a stirrer, and 1,4-dioxane (1 ml) was added thereto, followed by stirring at room temperature for 10 minutes. Tetrabutylammonium bromide (128.8mg, 0.4mmol) and the corresponding 2b (X) were weighed out 2 ＝I,R 1 = 4-CHO) (46.2mg, 0.2mmol), then 1ml CPME was added, and after sealing, reaction was carried out at room temperature for 36 hours under 455nm blue light irradiation with a yield of 98%.1b: 1 H NMR(400MHz, CDCl 3 ):δ9.98(s,1H),7.75(d,J＝8.4Hz,2H),7.69(d,J＝8.4Hz,2H)。
example 11:
1c(X 1 ＝Br,R 1 = 4-CN)
Weighing dry catalyst Ni (COD) in glove box 2 (5.5mg, 0.02mmol, 10mol%) and dtbbpy (6.4mg, 0.024mmol, 12mol%) were put into a 10ml dry clean schlenk tube equipped with a stirrer, and 1,4-dioxane (1 ml) was added thereto, followed by stirring at room temperature for 10 minutes. Tetrabutylammonium bromide (128.8mg, 0.4mmol), the corresponding 2c (X) was weighed out 2 ＝I,R 1 ＝4-CN)(45.8mg,0.2mmol) Then 1ml of CPME is added, and after sealing, the reaction is carried out for 36 hours at room temperature under the irradiation of 455nm blue light, and the yield is 96 percent. 1c: 1 H NMR(400MHz, CDCl 3 ):δ7.64(d,J＝8.1Hz,2H),7.52(d,J＝8.2Hz,2H)。
example 12:
1d(X 1 ＝Br,R 1 ＝4- t bu) preparation
Weighing dry catalyst Ni (COD) in glove box 2 (5.5mg, 0.02mmol, 10mol%) and dtbbpy (6.4mg, 0.024mmol, 12mol%) were put into a 10ml dry clean schlenk tube equipped with a stirrer, and 1,4-dioxane (1 ml) was added thereto, followed by stirring at room temperature for 10 minutes. Tetrabutylammonium bromide (128.8mg, 0.4mmol) and the corresponding 2d (X) were weighed out 2 ＝I,R 1 ＝4- t Bu) (52mg, 0.2mmol), followed by addition of 1ml of CPME, sealing and reaction at room temperature under blue light irradiation at 455nm for 36 hours with a yield of 99%.1d: 1 H NMR(400MHz, CDCl 3 ):δ7.41(d,J＝8.6Hz,2H),7.26(d,J＝8.6Hz,2H),1.30(s,9H)。
example 13:
1e(X 1 ＝Br,R 1 preparation of = 4-OMe)
Weighing dry catalyst Ni (COD) in glove box 2 (5.5mg, 0.02mmol, 10mol%) and dtbbpy (6.4mg, 0.024mmol, 12mol%) were put into a 10ml dry clean schlenk tube equipped with a stirrer, and 1,4-dioxane (1 ml) was added thereto, followed by stirring at room temperature for 10 minutes. Tetrabutylammonium bromide (128.8mg, 0.4mmol) and the corresponding 2e (X) were weighed out 2 ＝I,R 1 = 4-OMe) (46.8mg, 0.2mmol), followed by addition of 1ml CPME, and after sealing, reaction was carried out at room temperature for 36 hours under blue-light irradiation at 455nm, yield 79%.1e: 1 H NMR (400MHz,CDCl 3 ):δ7.37(d,J＝10.2Hz,2H),6.78(d,J＝9.0Hz,2H),3.78(s, 3H)。
example 14:
1f(X 1 ＝Br,R 1 preparation of = 3-Me)
Weighing dry catalyst Ni (COD) in glove box 2 (5.5mg, 0.02mmol, 10mol%) and dtbbpy (6.4mg, 0.024mmol, 12mol%) were put into a 10ml dry clean schlenk tube equipped with a stirrer, and 1,4-dioxane (1 ml) was added thereto, followed by stirring at room temperature for 10 minutes. Weighing tetrabutylammonium bromide (128)8mg, 0.4mmol), corresponding 2f (X) 2 ＝I,R 1 = 3-Me) (23.6 mg, 0.2mmol), followed by addition of 1ml of CPME, sealing and reaction at room temperature under 455nm blue light irradiation for 36 hours with a yield of 72%.1f: 1 H NMR(400MHz, CDCl 3 ):δ7.27-7.21(m,2H),7.07-7.02(m,2H),2.26(s,3H)。
example 15:
1g(X 1 ＝Br,R 1 preparation of =3,5-Me)
Weighing dry catalyst Ni (COD) in glove box 2 (5.5mg, 0.02mmol, 10mol%) and dtbbpy (6.4mg, 0.024mmol, 12mol%) were put into a 10ml dry clean schlenk tube equipped with a stirrer, and 1,4-dioxane (1 ml) was added thereto, followed by stirring at room temperature for 10 minutes. Tetrabutylammonium bromide (128.8mg, 0.4 mmol), the corresponding 2g (X) were weighed out 2 ＝I,R 1 =3,5-Me) (32.6mg, 0.2mmol), and 1ml of CPME was added, and after sealing, the reaction was carried out at room temperature under 455nm blue light irradiation for 36 hours with a yield of 89%.1g: 1 H NMR (400MHz,CDCl 3 ):δ7.14(s,2H),6.91(s,1H),2.29(s,6H)。
example 16:
1h(X 1 ＝Br,R 1 preparation of =2,6-Me)
Weighing dry catalyst Ni (COD) in glove box 2 (5.5mg, 0.02mmol, 10mol%) and dtbbpy (6.4mg, 0.024mmol, 12mol%) were put into a 10ml dry clean schlenk tube equipped with a stirrer, and 1,4-dioxane (1 ml) was added thereto, followed by stirring at room temperature for 10 minutes. Tetrabutylammonium bromide (128.8mg, 0.4mmol) was weighed in the corresponding 2h (X) 2 ＝I,R 1 =2,6-Me) (35.7mg, 0.2mmol), followed by addition of 1ml of CPME, sealing and reacting at room temperature for 36 hours under 455nm blue light irradiation, yield 97%.1h: 1 H NMR (400MHz,CDCl 3 ):7.11-7.05(m,3H),2.42(s,6H)。
example 17:
1i(X 1 ＝Br,R 1 preparation of = 2-Me)
Weighing dry catalyst Ni (COD) in glove box 2 (5.5 mg,0.02mmol, 10mol%) and dtbbpy (6.4 mg,0.024mmol, 12mol%) were put into a 10ml dry and clean schlenk tube equipped with a stirrer, and 1,4-dioxane (1 ml) was added thereto, followed by stirring at room temperature for 10 minutes. Weighing fourButylammonium bromide (128.8mg, 0.4mmol), corresponding to 2i (X) 2 ＝I,R 1 = 2-Me) (28.3mg, 0.2mmol), followed by addition of 1ml of CPME, sealing and reaction at room temperature under blue light irradiation at 455nm for 36 hours with a yield of 83%.1i: 1 H NMR(400MHz, CDCl 3 ):δ7.42(d,J＝8.0Hz,1H),7.12-7.08(m,2H),6.96-6.92(m,1H),2.30(s, 3H).
example 18:
3a(X 1 ＝Cl,R 1 preparation of = 4-Ph)
Weighing dry catalyst Ni (COD) in glove box 2 (5.5 mg,0.02mmol, 10mol%) and dtbbpy (6.4 mg,0.024mmol, 12mol%) were put into a 10ml dry and clean schlenk tube equipped with a stirrer, and 1,4-dioxane (1 ml) was added thereto, followed by stirring at room temperature for 10 minutes. Triethylbenzylammonium chloride (91mg, 0.4 mmol), the corresponding 2a (X) was weighed out 2 ＝I,R 1 = 4-Ph) (60mg, 0.2mmol), followed by addition of 1ml of CPME, sealing and reaction at room temperature under blue light irradiation at 455nm for 36 hours, yield 99%.3a: 1 H NMR(400MHz, CDCl 3 ):δ7.59-7.51(m,4H),7.49-7.34(m,5H)。
example 19:
3b(X 1 ＝Cl,R 1 = 4-CHO) preparation
Weighing dry catalyst Ni (COD) in glove box 2 (5.5mg, 0.02mmol, 10mol%) and dtbbpy (6.4mg, 0.024mmol, 12mol%) were put into a 10ml dry clean schlenk tube equipped with a stirrer, and 1,4-dioxane (1 ml) was added thereto, followed by stirring at room temperature for 10 minutes. Triethylbenzylammonium chloride (91mg, 0.4mmol), the corresponding 2b (X) was weighed out 2 ＝I,R 1 = 4-CHO) (46.4 mg, 0.2mmol), then 1ml CPME was supplemented, and after sealing reaction was performed at 60 ℃ for 36 hours under 455nm blue light irradiation with a yield of 89%.3b: 1 H NMR (400MHz,CDCl 3 ):δ9.99(s,1H),7.83(d,J＝8.4Hz,2H),7.52(d,J＝8.4Hz,2H)。
example 20:
3d(X 1 ＝Cl,R 1 ＝4- t bu) preparation
Weighing dry catalyst Ni (COD) in glove box 2 (5.5mg, 0.02mmol, 10mol%) and dtbbpy (6.4mg, 0.024mmol, 12mol%) in 10ml dry clean equipped with a stirrerTo a schlenk tube, 1,4-dioxane (1 ml) was added, and the mixture was stirred at room temperature for 10 minutes. Triethylbenzylammonium chloride (91mg, 0.4 mmol), corresponding 2d (X) was weighed out 2 ＝I,R 1 ＝4- t Bu) (52mg, 0.2mmol), followed by addition of 1ml of CPME, sealing and reaction at 60 ℃ for 36 hours under blue light irradiation at 455nm, yield 93%.3d: 1 H NMR(400MHz, CDCl 3 ):7.32(d,J＝8.7Hz,2H),7.27(d,J＝8.6Hz,2H),1.31(s,9H)。

Claims (4)

1. a method for preparing different halogenated aromatic hydrocarbons by visible light promoted nickel-catalyzed halogen exchange is characterized in that under the protection of nitrogen, a nickel source catalyst is added into a reaction solvent, bipyridyl is stirred for 10 minutes at room temperature, then aryl halide and sodium iodide, tetrabutylammonium bromide or triethylbenzylammonium chloride are added, and the mixture is stirred and irradiated for 12 to 48 hours at a proper temperature to obtain a halogen exchanged product; the specific reaction process is as follows:
Figure FDA0004084599520000011
wherein, X 1 Is bromine or chlorine; x 2 Is iodine or bromine; r is 1 Selected from methyl, tert-butyl, methoxy, amino, trifluoromethyl, trifluoromethoxy, aldehyde group, acetyl, cyano, phenyl, ester group;
the nickel source catalyst is Ni (cod) 2 ；
The solvent is cyclopentyl methyl ether or 1, 4-dioxane.
2. The process of claim 1 wherein the reaction temperature is from 25 to 70 ℃ and the molar ratio of substrate aryl halide to nickel source catalyst is from 10:1-20:1, the molar ratio of the substrate aryl halide to the bipyridine is 25:3-50:3, the concentration of the substrate is 0.1M, and the concentration of the metal salt iodine source is 0.2-0.6M.
3. Method according to claim 1, characterized in that an LED blue-light lamp with a wavelength range of 410 to 480nm is selected as the visible light source.
4. The process of claim 1 wherein the bipyridine is 4, 4-di-tert-butylbipyridine, 4-di-methylbipyridine, 4-di-methoxybipyridine, or 2, 2-bipyridine.
CN202210798650.XA 2022-07-08 2022-07-08 Method for preparing different halogenated aromatic hydrocarbons by visible light promoted nickel-catalyzed halogen exchange Active CN115010563B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210798650.XA CN115010563B (en) 2022-07-08 2022-07-08 Method for preparing different halogenated aromatic hydrocarbons by visible light promoted nickel-catalyzed halogen exchange

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210798650.XA CN115010563B (en) 2022-07-08 2022-07-08 Method for preparing different halogenated aromatic hydrocarbons by visible light promoted nickel-catalyzed halogen exchange

Publications (2)

Publication Number Publication Date
CN115010563A CN115010563A (en) 2022-09-06
CN115010563B true CN115010563B (en) 2023-03-31

Family

ID=83078687

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210798650.XA Active CN115010563B (en) 2022-07-08 2022-07-08 Method for preparing different halogenated aromatic hydrocarbons by visible light promoted nickel-catalyzed halogen exchange

Country Status (1)

Country Link
CN (1) CN115010563B (en)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110668913B (en) * 2019-09-16 2022-09-20 江苏三美化工有限公司 Preparation method of trifluoroethyl compound
CN111253207B (en) * 2020-03-05 2022-04-01 苏州大学 Preparation method of visible light catalyzed double-chlorine addition product of aromatic olefin
CN114380675B (en) * 2022-01-26 2024-06-11 苏州大学 Method for synthesizing aryl phenol by reacting halogenated aromatic hydrocarbon and phenol compound under induction of visible light

Also Published As

Publication number Publication date
CN115010563A (en) 2022-09-06

Similar Documents

Publication Publication Date Title
Hong et al. C− H bond carboxylation with carbon dioxide
CN1075050C (en) Process for preparing atomatic olefins
Li et al. From C (sp 2)–H to C (sp 3)–H: systematic studies on transition metal-catalyzed oxidative C–C formation
Yoshino et al. Cp* Co III-Catalyzed C2-Selective Addition of Indoles to Imines.
CN110467579B (en) Preparation method of 5-trifluoromethyl substituted 1,2, 4-triazole compound
CN108069934B (en) Method for preparing polyaromatic substituted naphthalene derivative by reaction of biphenyl type arone and tolane catalyzed by ruthenium
Zeng et al. Iridium/copper-cocatalyzed asymmetric ring opening reaction of azabenzonorbornadienes with amines
CN112573978B (en) High-efficiency halogenation synthesis method of aryl halide
Wang et al. Manganese/NaOPh co-catalyzed C2-selective C–H conjugate addition of indoles to α, β-unsaturated carbonyls
Rawat et al. Fixation of carbon dioxide to aryl/aromatic carboxylic acids
CN107973691B (en) Method for preparing polyaromatic substituted naphthalene derivative by cyclization reaction of aromatic ketone and tolane catalyzed by ruthenium and application
Zheng et al. Highly enantioselective Michael addition of malononitrile to α, β-unsaturated pyrazolamides catalyzed by a bifunctional thiourea
Yang et al. Exploiting the trifluoroethyl group as a precatalyst ligand in nickel-catalyzed Suzuki-type alkylations
CN115010563B (en) Method for preparing different halogenated aromatic hydrocarbons by visible light promoted nickel-catalyzed halogen exchange
Weseliński et al. A convenient preparation of 9H-Carbazole-3, 6-dicarbonitrile and 9H-Carbazole-3, 6-dicarboxylic acid
CN111454150B (en) Synthesis method of (S) -2-aryl propionate compound
CN108299340B (en) Method for synthesizing 2-fluoro-N-substituted aryl acetamide compound
WO2015170688A1 (en) Metal-supported porous coordination polymer catalyst
CN111484436A (en) Method for introducing isopentenyl group to C3 position of indole
CN111057080B (en) Preparation method of boron-containing indolinone derivative
CN112194559B (en) Synthesis method of chiral and achiral 2,2' -dihalogenated biaryl compound
Fu et al. ipso-Bromination/iodination of arylboronic acids: Poly (4-vinylpyridine)-Br2/I2 complexes as safe and efficient reagents
CN114436936A (en) Method for continuously preparing allene compounds by micro-flow field visible light catalytic reaction technology
CN109651344B (en) Benzofuran triarylmethane compounds and green catalytic synthesis method thereof
CN115745825B (en) Method for catalyzing amide alkylation reaction by using tridentate NNO nickel complex

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant