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[ CAS No. 58970-19-7 ]

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Chemical Structure| 58970-19-7
Chemical Structure| 58970-19-7
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CAS No. :58970-19-7 MDL No. :MFCD01318447
Formula : C13H11ClO Boiling Point : -
Linear Structure Formula :- InChI Key :-
M.W :218.68 g/mol Pubchem ID :-
Synonyms :

Safety of [ 58970-19-7 ]

Signal Word:Warning Class:
Precautionary Statements:P261-P264-P271-P280-P302+P352-P304+P340-P305+P351+P338-P312-P362-P403+P233-P501 UN#:
Hazard Statements:H315-H319-H335 Packing Group:
GHS Pictogram:

Application In Synthesis of [ 58970-19-7 ]

  • Downstream synthetic route of [ 58970-19-7 ]

[ 58970-19-7 ] Synthesis Path-Downstream   1~15

  • 1
  • [ 67-56-1 ]
  • [ 77290-72-3 ]
  • [ 58970-19-7 ]
YieldReaction ConditionsOperation in experiment
86% With iodine for 5h; Heating;
  • 2
  • [ 58970-19-7 ]
  • [ 75-36-5 ]
  • [ 77893-86-8 ]
YieldReaction ConditionsOperation in experiment
71% With aluminium trichloride In carbon disulfide
  • 3
  • [ 232946-70-2 ]
  • [ 58970-19-7 ]
YieldReaction ConditionsOperation in experiment
2 mg Stage #1: 4-{2-[(4'-methoxy-biphenyl-4-yl)-dimethyl-germanyl]-ethyl}-phenol With Argogel; tributylphosphine; diamide In benzene for 16h; Stage #2: With N-chloro-succinimide In tetrahydrofuran at 70℃; for 16h; Further stages.;
  • 4
  • 4-[2-dimethyl-(4,4'-biphenylmethoxy)germylethyl]phenyl ethoxyethyl ether [ No CAS ]
  • [ 58970-19-7 ]
YieldReaction ConditionsOperation in experiment
65% With N,N-dichloro-p-toluenesulfonamide In tetrahydrofuran at 70℃; for 14h;
  • 5
  • [ 4456-36-4 ]
  • [ 1679-18-1 ]
  • [ 58970-19-7 ]
YieldReaction ConditionsOperation in experiment
72% With bis-triphenylphosphine-palladium(II) chloride; sodium methylate In 1,2-dimethoxyethane; water at 50℃; for 5h;
  • 6
  • [ 637-87-6 ]
  • [ 5720-07-0 ]
  • [ 58970-19-7 ]
YieldReaction ConditionsOperation in experiment
98% With C43H54N2S; palladium diacetate; potassium carbonate In water; isopropyl alcohol at 100℃; for 4h; Aerobic condition; Sealed tube;
98% With potassium carbonate In ethanol; water at 50℃; for 1h; 2.4.1 Suzuki Cross-Coupling Reaction General procedure: A flame-dried 50mL round-bottom flask equipped with amagnetic stir bar and a rubber septum was charged with arylhalide (1.0mmol), phenyl boronic acid (1.1mmol), K2CO3(2.0mmol) and CL-salen-Pd(II) (0.5% mmol). The mixturewas stirred in Ethanol: H2O= 1:1 (5.0mL) at 50 underair atmosphere for 1h. The mixture was cooled to roomtemperature, quenched with water (5mL), and diluted withethyl acetate (5mL). The layers were separated, and theaqueous layer was extracted with 2 × 5mL of ethyl acetate.The combined organic extracts were dried over anhydrousmagnesium sulfate, filtered, and concentrated in vacuo.Finally, the product was purified by column chromatography.
96% With caesium carbonate In water; N,N-dimethyl-formamide at 20℃; Inert atmosphere; General procedure for Suzuki cross coupling reaction General procedure: The Suzuki coupling reactions were carried out in a test tube (13 mm) using an organic synthesizer. Aryl iodides, bromides and chlorides (0.1 mmol) base (150 mol%), arylboronic acid (0.15 mmol) and Pd catalysts 3-5 atom% were placed in a test tube. The argon gas was supplied from the balloon with argon exchange 2 times without degassing. Solvent was added and stirred at 1000 rpm at specified temperature for the desired time. Completion of the reaction was monitored by TLC. After completion, the reaction was cooled and quenched by 1M HCl, extract with EtOAc. The organic layer was evaporated, dried and the yields were reported as NMR or isolated yield after purification by silica gel column chromatography (eluted with EtOAc/Hexane). The products were confirmed by 1H NMR spectra and mass comparing with the pure, commercially available compounds and reported NMR in the literature which exactly matched with the reported values.1-18
95% With 2,2'-diamino-6,6'-dimethylbiphenyl; potassium carbonate; copper(II) oxide In N,N-dimethyl-formamide at 130℃; for 48h; Inert atmosphere;
95% With potassium carbonate In dimethyl sulfoxide at 120℃;
95% With palladium diacetate In ethanol at 20℃; for 0.0833333h; chemoselective reaction;
94% With C17H23Br2N3Pd; potassium <i>tert</i>-butylate In water at 20℃; for 24h; Inert atmosphere; 2.2. General procedure for the Pd(II)-NHC complex 1-catalyzed Suzuki-Miyaura cross-coupling reaction of arylboronic acids with aryl iodides and bromides General procedure: (If aryl halide is a liquid) under N2 atmosphere, arylboronic acid 3 (0.6 mmol), Pd(II)-NHC 1 (1.0 mol%), KOBut (1.0 mmol) and H2O (2.0 mL) were added into a Schlenk tube, then aryl halide 2 (0.5 mmol) was added. The mixture was stirred vigorously at room temperature for 24 h. Then the solventwas removed under reducedpressure and the residue was purified by a flash column chromatography (SiO2) to give the pure product.(If aryl halide is a solid) under N2 atmosphere, aryl halide 2 (0.5 mmol), arylboronic acid 3 (0.6 mmol), Pd(II)-NHC 1 (1.0 mol%), KOBut (1.0 mmol) and H2O (2.0 mL) were added into a Schlenk reaction tube. The mixture was stirred vigorously at room temperature for 24 h. Then the solventwas removed under reduced pressure and the residue was purified by a flash column chromatography (SiO2) to give the pure product.
93% With potassium carbonate In ethanol; water at 80℃; for 3.5h;
92% With 2,2'-diamino-6,6'-dimethylbiphenyl; palladium diacetate; caesium carbonate In tetrahydrofuran at 40℃; for 12h; Inert atmosphere;
90% With trihexyl(tetradecyl)phosphonium chloride; potassium phosphate In toluene at 50℃; for 1h;
89% With 4-(benzylthio)-N,N,N-trimethylbenzenammonium chloride; palladium diacetate; sodium carbonate In water at 80℃; for 12h; Schlenk technique; Inert atmosphere; 4.6 General procedure for the Suzuki-Miyaura reaction General procedure: A mixture of aryl halide (0.5mmol), arylboronic acid (0.75mmol), Pd(OAc)2 (2mol%), L1 (2mol%), Na2CO3 (1mmol), and deoxygenated H2O (3mL) was loaded into a 25mL round bottom flask. The mixture was stirred at 80°C for 12h in N2. Then it was cooled to ambient temperature, and extracted three times with diethyl ether (3×5mL). The combined organic layer was washed with brine (20mL) and dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by flash column chromatography using petroleum ether and ethyl acetate as the eluent.
85% With potassium carbonate In dimethyl sulfoxide at 120℃; for 0.166667h; 2.2 General procedure 1 (for the synthesis ofbiphenyls 3) General procedure: In an oven-dried Schlenk tube iodoarenes 1 (0.25 mmol), arylboroicacids 2 (0.5 mmol), PdO/GO nano catalyst (5 mol%),K2CO3 (0.5 mmol) and solvent (DMSO) (1.0 mL) wereadded. The resulting reaction mixture was stirred at 120 °Cfor 5-30 min. The progress of the reaction was monitoredby TLC. After completion of reaction, the reaction mixturewas allowed to cool to room temperature, then diluted with(approximately 10 mL) ethyl acetate and NH4Cl solution(approximately 10mL)was added followed by extractionwithethyl acetate. The organic layers were dried with Na2SO4 andconcentrated in reduced vacuum. Purification of the residue bysilica gel column chromatography using distilled petroleumether/ethyl acetate as the eluent furnished the biphenyls.
68% With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In water; N,N-dimethyl-formamide at 85℃; for 24h; Inert atmosphere; Schlenk technique;
37% With potassium carbonate In tetrahydrofuran at 120℃; for 24h;

Reference: [1]Location in patent: scheme or table Li, Hong-Ling; Wu, Zhi-Sheng; Yang, Min; Qi, Yan-Xing [Catalysis Letters, 2010, vol. 137, # 1-2, p. 69 - 73]
[2]Sun, Peng; Yang, Jiaojiao; Chen, Chunxia; Xie, Kaijun; Peng, Jinsong [Catalysis Letters, 2020, vol. 150, # 10, p. 2900 - 2910]
[3]Karanjit, Sangita; Kashihara, Masaya; Nakayama, Atsushi; Shrestha, Lok Kumar; Ariga, Katsuhiko; Namba, Kosuke [Tetrahedron, 2018, vol. 74, # 9, p. 948 - 954]
[4]Location in patent: experimental part Ye, Yue-Mei; Wang, Bin-Bin; Ma, Dan; Shao, Li-Xiong; Lu, Jian-Mei [Catalysis Letters, 2010, vol. 139, # 3-4, p. 141 - 144]
[5]Lakshminarayana, Bhairi; Chakraborty, Jhonti; Satyanarayana; Subrahmanyam, Ch. [RSC Advances, 2018, vol. 8, # 37, p. 21030 - 21039]
[6]Appa, Rama Moorhy; Prasad, S. Siva; Lakshmidevi, Jangam; Naidu, Bandameeda Ramesh; Narasimhulu, Manchala; Venkateswarlu, Katta [Applied Organometallic Chemistry, 2019, vol. 33, # 10]
[7]Location in patent: experimental part Tang, Yi-Qiang; Lv, Huan; Lu, Jian-Mei; Shao, Li-Xiong [Journal of Organometallic Chemistry, 2011, vol. 696, # 13, p. 2576 - 2579]
[8]Dasari, Gopala Krishna; Sunkara, Satyaveni; Gadupudi, Purna Chandra Rao [Inorganic and Nano-Metal Chemistry, 2020, vol. 50, # 9, p. 753 - 763]
[9]Location in patent: experimental part Lu, Jian-Mei; Ma, Hui; Li, Sha-Sha; Ma, Dan; Shao, Li-Xiong [Tetrahedron, 2010, vol. 66, # 27-28, p. 5185 - 5189]
[10]McNulty, James; Capretta, Alfredo; Wilson, Jeff; Dyck, Jeff; Adjabeng, George; Robertson, Al [Chemical Communications, 2002, # 17, p. 1986 - 1987]
[11]Liu, De-Xian; Gong, Wei-Jie; Li, Hong-Xi; Gao, Jun; Li, Fei-Long; Lang, Jian-Ping [Tetrahedron, 2014, vol. 70, # 21, p. 3385 - 3389]
[12]Lakshminarayana, Bhairi; Mahendar, Lodi; Chakraborty, Jhonti; Satyanarayana, Gedu; Subrahmanyam, Ch [Journal of Chemical Sciences, 2018, vol. 130, # 5]
[13]Li, Jinpeng; Huang, Changyu; Wen, Daheng; Zheng, Qingshu; Tu, Bo; Tu, Tao [Organic Letters, 2021, vol. 23, # 3, p. 687 - 691]
[14]Liu, Jia; Chen, Zhongxin; Liu, Cuibo; Zhang, Bao; Du, Yonghua; Liu, Chen-Fei; Ma, Lu; Xi, Shibo; Li, Runlai; Zhao, Xiaoxu; Song, Jingting; Sui, Xin Zhi; Yu, Wei; Miao, Ling; Jiang, Jianjun; Koh, Ming Joo; Loh, Kian Ping [Journal of Materials Chemistry A, 2021, vol. 9, # 18, p. 11427 - 11432]
  • 7
  • [ 696-62-8 ]
  • [ 1679-18-1 ]
  • [ 58970-19-7 ]
YieldReaction ConditionsOperation in experiment
99% With potassium carbonate In water monomer at 50℃; for 12h;
98% With bis(acetonitrile)palladium(II) chloride; C10H11N3S; potassium carbonate In water monomer; N,N-dimethyl-formamide at 20℃; for 1h; Schlenk technique; Inert atmosphere; 4.3. Representative procedure for the synthesis of compound 3aa General procedure: An oven-dried Schlenk tube was charged with 2a (1.2 mmol), Pd(CH3CN)2Cl2 (0.1 mol%), L1(0.1 mol%), anhydrous K2CO3 (2 mmol).The Schlenk tube was backfilled with argon for three times. Then,DMF/H2O (2:1) (3 mL) was added by syringe, followed by additionof 1a (1 mmol) in a similar manner (solids were added with otherreagents before evacuation). The reaction was stirred in room temperatureand was monitored by TLC. After 1 h, the reaction mixturewas added water (50 mL), and then extracted with ethyl acetate(50 mL x 3). The combined organic layer was washed with brineand was dried over anhydrous Na2SO4. After filtered and concentratedunder reduced pressure, the residue was purified by columnchromatography on silica gel (Petroleum ether as eluent) to yieldthe product.
98% With Ti0.97Pd0.03O1.97; potassium carbonate In water monomer at 100℃; for 6h; 9.3 Typical experimental procedure for the palladium-catalyzed suzuki cross-coupling reaction in water General procedure: A mixture of aryl halide 1 (0.4mmol), arylboronic acid 2 (0.8mmol), Ti0.97Pd0.03O1.97 (nanoparticles; 10wt %), K2CO3 (110mg, 0.8mmol) in water (2mL) was stirred at 100°C for 6h. After the completion of the reaction, diethyl ether (15ml x 3 times) was poured into the mixture, washed with water (15mL), extracted with diethyl ether (3×20mL), dried over anhydrous Na2SO4 and evaporated under vacuum; the residue was purified by column chromatography (petroleum ether or petroleum ether/ethyl acetate) to obtain the desired coupled product.
97% Stage #1: para-iodoanisole In N,N-dimethyl-formamide at 90℃; for 0.833333h; Microwave irradiation; Stage #2: 4-Chlorophenylboronic acid With potassium carbonate In N,N-dimethyl-formamide at 102℃; for 1h; Microwave irradiation;
96% With C20H16N4O5(2-)*Pd(2+); potassium carbonate In water monomer at 70℃; for 2h; Reflux;
96% With C38H38N6O2Pd(2+)*2Cl(1-); potassium carbonate In water monomer at 20℃; for 2h;
95% With polymer-based palladium; anhydrous sodium carbonate In water monomer; N,N-dimethyl-formamide at 50℃; for 1h;
95% With potassium hydroxide In methanol at 50℃; for 12h;
93% With Cell-OPPH2-Pd(0); potassium carbonate In ethanol; water monomer for 0.25h; Reflux;
93% With potassium carbonate In ethanol at 78℃; for 1h; Air atmosphere;
92% With potassium carbonate In ethanol at 80℃; for 12h;
92% With potassium carbonate In ethanol; water monomer at 65℃; for 3h;
92% With potassium carbonate In water monomer at 90℃; for 0.833333h; 2.3 General Procedure for Suzuki Coupling Reaction General procedure: Mixture of iodobenzene (0.5 mmol), boronic acid(0.75 mmol), K2CO3 (1.25 mmol), PdNP-PG catalyst(0.1 mol %), and water as a solvent (2 mL) was stirred at 90 °C for appropriate time as indicated in Table 1 entry 5.The progress of the reaction was monitored by TLC. The reaction mass was cooled after completion of the reaction and the catalyst was separated by filtration. The product was extracted from aqueous layer by using 10 mL ethylacetate. The combined organic layer was dried on anhydrous sodium sulphate, concentrated under reduced pressure and was purified by column chromatography on silicagel (Hexane/EtOAc: 98:2) to get the product.
91% With dicyclohexyl({2’,6’-dimethoxy-[1,1‘-biphenyl]-2-yl})phosphane; copper (I) iodide In ethanol at 80℃; for 2h;
90% With potassium carbonate In ethanol; water monomer at 20℃; for 1h; Green chemistry; 2.4 General procedure for Suzuki-Miyaura cross-coupling reaction General procedure: In a 10 mL glass vial equipped with a cap containing 5 mL of ethanol:water (1:1) mixture, aryl halide (1 equiv), phenylboronic acid (1.1 equiv), K2CO3 (2.5 equiv) were added followed by dipping of the dip catalyst into the reaction mixture which was then stirred magnetically at room temperature for required time. The progress of the reaction was monitored by thin layer chromatography (TLC). After reaction completion, the dip catalyst was simply removed from the reaction mass and washed with ethanol (1 x 5 mL) and water (1 x 5 mL) and was reused without purifying further. The product was extracted using dichloromethane (2 x 10 mL) and the combined organic layer was subjected to water wash (2 x 10 mL) followed by drying of the organic layer over Na2SO4. The dried organic layer was concentrated in vacuo, and the product was purified by column chromatography using n-hexane and ethyl acetate as eluents to afford the corresponding products in good to excellent yields. All the coupled products were known molecules and were confirmed by comparing with our previous standards (Kandathil et al., 2017; Vishal et al., 2017).
89% With anhydrous sodium carbonate; triphenylphosphine In water monomer at 80℃; for 18h; Schlenk technique; Suzuki-Miyaura cross-coupling reaction General procedure: A mixture of aryl halide (0.25 mmol), phenylboronicacid (0.3 mmol), Na2CO3 (0.25 mmol), PPh3 (0.025 mmol)and Pd(at)PAAs-CD (0.5 mg, 0.2 mol% Pd per mol of arylhalide) were placed into a 10 mL Schlenck tube with1 mL H2O. The reaction mixture was reacted at 80 °C for18 h, and the reaction progress was monitored via gaschromatography mass spectrometry (GC-MS). The reactionmixture was allowed to cool to room temperature, andthen 3 mL water was added, and the product was extractedwith ethyl acetate (3 mL × 3). The organic layers werecombined and dried over anhydrous Na2SO4 and solventswere evaporated via rotary evaporator. The crude productwas purified by column chromatography (200-300 meshsilica) using a mixture of petroleum ether/ethyl acetate(10:1, v:v) as eluent. The structures of the products wereconfirmed by 1H NMR and 13C NMR spectroscopies.
85% With anhydrous sodium carbonate In ethanol; water monomer at 20℃; for 0.16h; Green chemistry;
84% With 1-[2-(2-hydroxybenzylideneamino)ethyl]-3-methyl-3H-imidazol-3-ium hexafluorophosphate; potassium carbonate; palladium (II) chloride In ethanol for 0.5h; Reflux;
77% With anhydrous sodium carbonate In methanol at 20℃; for 24h;
74% With anhydrous sodium carbonate In ethanol; water monomer at 20℃; for 0.833333h; Green chemistry; 2.8 General Procedure for Suzuki-Miyaura Cross-Coupling Reaction General procedure: To a solution of aryl halide (1 equiv.), aryl boronic acid (1.1 equiv.) and sodium carbonate (2.5 equiv.) in ethanol (EtOH):water (H2O) (1:1) (5mL), hexagonal boron nitride tethered N-heterocyclic carbene-palladium(II) complex (h-BN(at)NHC-Pd) (0.02mol% Pd) was added and stirred at room temperature for required period of time. On completionof the reaction monitored by TLC, the h-BN(at)NHC-Pd heterogeneous catalyst was separated from the reaction massby centrifugation. DCM (20mL) was added to the residual reaction mixture. Then DCM layer was separated using a separatory funnel. The DCM layer was washed with water, brine solution and dried over anhydrous Na2SO4.The driedDCM layer was concentrated in vacuum and purified through column chromatography using hexane and ethyl acetate as eluents to get the corresponding products in good to excellent yields. All the cross-coupled products were analyzed by 1H NMR spectroscopy and compared with the standards.
72% With potassium carbonate In dimethyl sulfoxide at 120℃;
51% Stage #1: para-iodoanisole; 4-Chlorophenylboronic acid With tripotassium phosphate tribasic; Ni(NO3)2·6H2O; 1,1'-((1H-pyrrole-2,5-diyl)bis(methylene))bis(3-methyl-1H-imidazol-3-ium) diiodide In toluene at 20℃; for 0.0833333h; Sealed tube; Stage #2: In toluene at 160℃; for 3h; Sealed tube; 2. General procedure for the Suzuki-Miyaura cross-coupling reactions General procedure: Aryl iodide (1.0 mmol), arylboronic acid (2.0 mmol), Ni(NO3)26H2O (0.05 mmol), pre-ligand Pre-L1(0.05 mmol), base (3.0 mmol), and toluene (3 mL) were added to a glass tube, which was then sealed with aPTFE cap. After the reaction mixture was stirred vigorously at room temperature for 5 min, the sealed glasstube with the reaction mixture was placed in a Radleys Carousel 12 Plus Reaction Station, which waspreheated to the described temperature. After the reaction was stirred for the required time and then cooleddown to room temperature, water (10 mL) was added to the reaction mixture. The resulting mixture wasextracted with ethyl acetate (3 x 10 mL). The combined organic layers were dried over anhydrous Na2SO4,filtered and concentrated to dryness. The remaining residue was analyzed by GC (Table 1) or purified byflash chromatography on silica gel with ethyl acetate-hexanes (0-20% ethyl acetate in hexanes).
98 %Chromat. With potassium carbonate In ethanol at 80℃; for 12h; Inert atmosphere;
> 99 %Chromat. With potassium carbonate In ethanol at 80℃; for 12h;
96 %Chromat. With potassium carbonate In N,N-dimethyl-formamide at 100℃; for 12h; Sealed tube;
With tripotassium phosphate tribasic; C10H20N2O4Pd In ethanol; water monomer at 100℃; for 5h;

Reference: [1]Uozumi, Yasuhiro; Nakai, Yasushi [Organic Letters, 2002, vol. 4, # 17, p. 2997 - 3000]
[2]Yan, Qiong; Zheng, Lei; Li, Miaomiao; Chen, Yunfeng [Journal of Catalysis, 2019, vol. 376, p. 101 - 105]
[3]Bhat K, Shrikanth; Lanke, Veeranjaneyulu; Prasad, Jagadeesh Dasappa; Prabhu, Kandikere Ramaiah [Applied Catalysis A: General, 2020, vol. 596]
[4]Al-Amin, Mohammad; Akimoto, Masayoshi; Tameno, Tsuyoshi; Ohki, Yuuta; Takahashi, Naoyuki; Hoshiya, Naoyuki; Shuto, Satoshi; Arisawa, Mitsuhiro [Green Chemistry, 2013, vol. 15, # 5, p. 1142 - 1145]
[5]Wang, Junke; Zong, Yingxiao; Wang, Xicun; Hu, Yulai; Yue, Guoren; Pan, Yi [Green Chemistry, 2016, vol. 18, # 4, p. 967 - 973]
[6]Zong, Yingxiao; Wang, Junke; He, Yubi; Yue, Guoren; Wang, Xicun; Pan, Yi [RSC Advances, 2016, vol. 6, # 92, p. 89621 - 89626]
[7]Kim, Jong-Ho; Kim, Jung-Woo; Shokouhimehr, Mohammadreza; Lee, Yoon-Sik [Journal of Organic Chemistry, 2005, vol. 70, # 17, p. 6714 - 6720]
[8]Tanaka, Shinya; Kaneko, Tetsuro; Asao, Naoki; Yamamoto, Yoshinori; Chen, Mingwei; Zhang, Wei; Inoue, Akihisa [Chemical Communications, 2011, vol. 47, # 21, p. 5985 - 5987]
[9]Location in patent: experimental part Du, Qingwei; Li, Yiqun [Beilstein Journal of Organic Chemistry, 2011, vol. 7, p. 378 - 385]
[10]Location in patent: experimental part Zhou, Bo; Li, Yi-Qun [E-Journal of Chemistry, 2011, vol. 8, # 4, p. 1490 - 1497]
[11]Hoshiya, Naoyuki; Shuto, Satoshi; Arisawa, Mitsuhiro [Advanced Synthesis and Catalysis, 2011, vol. 353, # 5, p. 743 - 748]
[12]Tong, Jinhui; Wang, Haiyan; Cai, Xiaodong; Zhang, Qianping; Ma, Hengchang; Lei, Ziqiang [Applied Organometallic Chemistry, 2014, vol. 28, # 2, p. 95 - 100]
[13]Balsane, Kishor E.; Shelkar, Radheshyam S.; Nagarkar, Jayashree M. [Catalysis Letters, 2015, vol. 145, # 10, p. 1817 - 1824]
[14]Lakshmidevi, Jangam; Naidu, Bandameeda Ramesh; Venkateswarlu, Katta [Molecular catalysis, 2022, vol. 522]
[15]Kandathil, Vishal; Kempasiddaiah, Manjunatha; B. S., Sasidhar; Patil, Siddappa A. [Carbohydrate Polymers, 2019, vol. 223]
[16]Zhang, Wei; Yao, Zi-Jian; Deng, Wei [Journal of the Brazilian Chemical Society, 2019, vol. 30, # 8, p. 1667 - 1677]
[17]Kempasiddhaiah, Manjunatha; Kandathil, Vishal; Dateer, Ramesh B.; Sasidhar, Balappa S.; Patil, Shivaputra A.; Patil, Siddappa A. [Applied Organometallic Chemistry, 2019, vol. 33, # 5]
[18]Location in patent: experimental part Li, Bin; Li, Yi-Qun; Zheng, Jia [ARKIVOC, 2010, vol. 2010, # 9, p. 163 - 170]
[19]Kantam, M. Lakshmi; Kumar, K. B. Shiva; Srinivas; Sreedhar [Advanced Synthesis and Catalysis, 2007, vol. 349, # 7, p. 1141 - 1149]
[20]Antony, Arnet Maria; Kandathil, Vishal; Kempasiddaiah, Manjunatha; Sasidhar; Patil, Shivaputra A.; Patil, Siddappa A. [Catalysis Letters, 2021, vol. 151, # 5, p. 1293 - 1308]
[21]Lakshminarayana, Bhairi; Chakraborty, Jhonti; Satyanarayana; Subrahmanyam, Ch. [RSC Advances, 2018, vol. 8, # 37, p. 21030 - 21039]
[22]Guo, Zhifo; Lei, Xiangyang [Journal of Organometallic Chemistry, 2021, vol. 953]
[23]Hoshiya, Naoyuki; Shimoda, Masahiko; Yoshikawa, Hideki; Yamashita, Yoshiyuki; Shuto, Satoshi; Arisawa, Mitsuhiro [Journal of the American Chemical Society, 2010, vol. 132, # 21, p. 7270 - 7272]
[24]Al-Amin, Mohammad; Arai, Satoshi; Hoshiya, Naoyoki; Honma, Tetsuo; Tamenori, Yusuke; Sato, Takatoshi; Yokoyama, Mami; Ishii, Akira; Takeuchi, Masashi; Maruko, Tomohiro; Shuto, Satoshi; Arisawa, Mitsuhiro [Journal of Organic Chemistry, 2013, vol. 78, # 15, p. 7575 - 7581]
[25]Hu, Qiyan; Liu, Xiaowang; Tang, Lin; Min, Dewen; Shi, Tianchao; Zhang, Wu [RSC Advances, 2017, vol. 7, # 13, p. 7964 - 7972]
[26]Quibell, Jacob M.; Duan, Guojian; Perry, Gregory J.P.; Larrosa, Igor [Chemical Communications, 2019, vol. 55, # 45, p. 6445 - 6448]
  • 8
  • [ 5720-07-0 ]
  • 1-(4-chlorophenyl)-2-(pyrrolidin-1-yl)diazene [ No CAS ]
  • [ 58970-19-7 ]
YieldReaction ConditionsOperation in experiment
73% With boron trifluoride diethyl etherate; palladium diacetate In 1,4-dioxane at 20℃; for 10h; Inert atmosphere; chemoselective reaction;
68% With tri-tert-butyl phosphine; boron trifluoride diethyl etherate In 1,2-dimethoxyethane; hexane at 20℃; for 1h;
  • 9
  • [ 5720-07-0 ]
  • [ 106-47-8 ]
  • [ 58970-19-7 ]
YieldReaction ConditionsOperation in experiment
75% With tris-(dibenzylideneacetone)dipalladium(0); tert.-butylnitrite; trifuran-2-yl-phosphane; acetic acid In N,N-dimethyl-formamide at 90℃; for 8h; Inert atmosphere; General procedure. Pd2dba3 (23 mg, 2.5 mol %), P (2-furyl)3 (46 mg, 20 mol %), 4-methoxybenzeneboronic acid 2b (182 mg, 1.2 equiv), and p-toluidine 1b (107 mg, 1 mmol) were weighed in a 25 mL Schlenk round bottle flask under nitrogen atmosphere. The system was degassed four times by oil pump. DMF (4 mL), tBuONO (134 mg, 1.3 equiv), and HOAc (60 mg, 1.0 equiv) were then added in succession by syringe. The resulting reaction mixture was allowed to stir at 90 °C for 8 h. The solution was then concentrated under reduced pressure and the crude residue was purified by flash column chromatography with petroleum ether to give 4-methoxy-4'-methylbiphenyl 3b (152 mg, 77%).
67% Stage #1: 4-chloro-aniline With tert.-butylnitrite; boron trifluoride diethyl etherate at -15 - 5℃; for 0.583333h; Stage #2: 4-methoxyphenylboronic acid With (R,R)-N,N'-(2-MeC6H4)2-N,N'-(cyclohexane-1,2-diyl)thiourea In methanol at 20℃; for 4h;
56% Stage #1: 4-chloro-aniline With tert.-butylnitrite; boron trifluoride diethyl etherate In methanol at 0℃; for 0.5h; Schlenk technique; Stage #2: 4-methoxyphenylboronic acid In methanol at 0 - 60℃; for 5h; Schlenk technique;
  • 10
  • [ 104-92-7 ]
  • [ 1679-18-1 ]
  • [ 58970-19-7 ]
YieldReaction ConditionsOperation in experiment
99% With C28H38Cl2N2O6PdS2(2-)*2Na(1+); potassium carbonate In ethanol; water monomer at 70℃;
99% With C34H35ClN5OPd*F6P(1-); potassium hydroxide In 1,4-dioxane at 75℃; for 5h; Inert atmosphere;
99% With tripotassium phosphate tribasic; palladium diacetate; 2-benzothiazolecarboxaldehyde N,N-diphenylhydrazone In water monomer at 96℃; for 0.25h; Irradiation;
98% With potassium carbonate In methanol; water monomer at 80℃; for 6h;
98% With tripotassium phosphate tribasic In water monomer; N,N-dimethyl-formamide at 100℃; for 0.5h; 4.5. General procedures for Suzuki-Miyaura reactions using 0.1 mol% NHC-Pd/FSG General procedure: A sealed tube was charged with aryl halide (1.0 mmol), arylboronic acid (1.5 mmol), K3PO4 (2.0 mmol), DMF/H2O (v/v = 1:1, 2 mL) and catalyst (0.1 mol% Pd), the mixture was stirred at 100 °C for a certain time under air atmosphere. After being cooled to room temperature, the mixture was diluted with CH2Cl2 and filtered. The organic phase was separated and dried over Na2SO4. The solvent was removed under vacuum and the residual was purified by column chromatography on silica gel with EtOAc/petroleum ether as eluent.
98% Stage #1: 1-bromo-4-methoxy-benzene In N,N-dimethyl-formamide at 90℃; for 0.833333h; Microwave irradiation; Stage #2: 4-Chlorophenylboronic acid With potassium carbonate In N,N-dimethyl-formamide at 102℃; for 1h; Microwave irradiation;
98% With palladium diacetate In ethanol at 20℃; for 0.166667h;
97% With C21H28N2; potassium carbonate; palladium (II) chloride In water monomer; N,N-dimethyl-formamide at 60℃; for 2h; 2.3 General procedure for Suzuki-Miyaura reaction General procedure: In a round bottle, ligand or palladium complexes (1 mol% mmol), aryl halides (1.0 mmol), arylboronic acid (1.2 mmol), K2CO3 (2.0 mmol) and 4 mL of DMF and 1 mL of H2O were added with a magnetic stir bar. The reaction mixture was carried out at the described temperature for the required time, and then the solvent was removed under reduced pressure. The residual was diluted with Et2O (5 mL), followed by extraction twice (2 × 5mL) with Et2O. The organic layer was dried with anhydrous MgSO4, filtered and evaporated under vacuum. The crude products were purified by silica-gel column chromatography using petroleum ether-ethyl acetate (20/1) as an eluent, and the isolated yield was then calculated based on the feeding of the aryl halide. The isolated corresponding products were characterized by 1H NMR and 13C NMR.
97% With C22H26N2O6Pd2; potassium carbonate In isopropanol at 20℃; for 15h;
97% With Cu0.98Pd0.02Fe2O4; potassium carbonate In ethanol; water monomer at 80℃; for 12h; 2.3 Suzuki coupling reaction process General procedure: All Suzuki coupling reactions were carried out in a 10mL round bottom flask equipped with a reflux condenser. In a typical experiment, 0.5mmol of aryl halide, 0.6mmol of phenylboronic acid, 1.0mmol of base and catalyst, 1.0mL solvents were added to the flask. The resulting mixture was stirred in an oil bath at the specified temperature for desired time. The reaction was monitored by thin layer chromatography (TLC). After completion of the reaction, the reaction mixture was cooled to room temperature and the catalyst was recovered by external magnet and washed with ethanol. The reaction mixture was diluted with water and extracted with ethyl acetate for three times. The organic layers were combined, dried over MgSO4, filtered and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel to give the pure products. The identities of the products were confirmed by 1H NMR and 13C NMR spectra.
97% With C20H16N4O5(2-)*Pd(2+); potassium carbonate In water monomer at 70℃; for 4h; Reflux;
96% With tripotassium phosphate tribasic In toluene at 110℃; for 3h;
96% With Cs2CO3 In toluene at 80℃; for 24h; 3.5 Example 3; Suzuki-Miyaura Cross-Coupling Reaction of Aryl Halides with Arylboronic Acids; The Suzuki-Miyaura reaction is typically co-catalyzed by alkyl phosphines. This Continued interest with triaminophosphine ligands prompted testing the efficacy of a new bicyclic triaminophosphine ligand 2 in palladium-catalyzed Suzuki-Miyaura reactions. Preliminary tests have revealed that the Pd(OAc)2/2 catalyst system is highly active in the Suzuki-Miyaura reaction of aryl bromides with arylboronic acids. The results are described in Table 7 below. In a typical reaction procedure, an oven-dried Schlenk flask equipped with a magnetic stirring bar was charged with Pd(OAc)2 (2 mol %), Cs2CO3 (2.0 mmol), arylboronic acid (1.5 mmol), aryl bromide (1.0 mmol) and ligand 2 (4 mol %). The flask was capped with a rubber septum, evacuated and then flushed with argon. This cycle was repeated three times. Toluene (3 mL) was then added by syringe. The flask was immersed in an oil bath preheated to 80° C. Upon complete consumption of the starting material (24 hours) as determined by TLC analysis, the mixture was cooled to room temperature, adsorbed onto silica gel and the desired biaryl compound was isolated by column chromatography (hexanes/ethyl acetate as eluents).
96% With potassium carbonate In water monomer at 50℃; for 2.5h; Green chemistry; General procedure for the Suzuki-Miyaura reaction General procedure: Forthe Suzuki-Miyaura reaction, a 50 mL round-bottomed flask was charged with aryl halide(0.5 mmol), arylboronic acid (0.65 mmol), K2CO3 (1 mmol), catalyst (0.002 g; 0.0005 mmol ofPd) and water (4 mL) and stirred at appropriate temperature. The progress of the reaction wasmonitored by thin layer chromatography using aluminum coated TLC plates (Merck) underUV light. At the end of reaction, the mixture was cooled down to room temperature and theproduct diluted with water (10 mL) and extracted with ether (3 x 15 mL). The combinedextract was washed with brine (3 x 15 mL) and dried over Na2SO4. After evaporation of the solventunder reduced pressure, the residue was subjected to column chromatography with ethylacetate/hexane (1:9) as eluent to get the desired product.
96% With sodium hydroxide In water monomer at 80℃; for 0.5h; Inert atmosphere; Green chemistry; 6. General procedure for Suzuki-Miyaura reaction General procedure: 5 mL distilled water was taken in a 25 mL round bottom flask, equipped with a magnetic bar and a water condenser, and deoxygenated with nitrogen gas for 5 min. Aryl halide (1 mmol), arylboronic acid (1.2 mmol), NaOH (1.2 mmol) and Pd-γ-Fe2O3 (20 mg) were added to it and allowed to stir at 80 °C under nitrogen atmosphere. The progress of the reaction was monitored by TLC. After completion of the reaction, the catalyst was recovered using an external magnet. The reaction mixture was extracted with EtOAc (3 x 10 mL) and the combined organic layer was washed with water, brine solution and dried over anhydrous Na2SO4. The crude product was concentrated in a rotary evaporator and purified by column chromatography. The purified compounds were characterized by 1H and 13C NMR.
96% With bis(acetonitrile)palladium(II) chloride; C10H11N3S; potassium carbonate In water monomer; N,N-dimethyl-formamide at 20℃; for 1h; Schlenk technique; Inert atmosphere; 4.3. Representative procedure for the synthesis of compound 3aa General procedure: An oven-dried Schlenk tube was charged with 2a (1.2 mmol), Pd(CH3CN)2Cl2 (0.1 mol%), L1(0.1 mol%), anhydrous K2CO3 (2 mmol).The Schlenk tube was backfilled with argon for three times. Then,DMF/H2O (2:1) (3 mL) was added by syringe, followed by additionof 1a (1 mmol) in a similar manner (solids were added with otherreagents before evacuation). The reaction was stirred in room temperatureand was monitored by TLC. After 1 h, the reaction mixturewas added water (50 mL), and then extracted with ethyl acetate(50 mL x 3). The combined organic layer was washed with brineand was dried over anhydrous Na2SO4. After filtered and concentratedunder reduced pressure, the residue was purified by columnchromatography on silica gel (Petroleum ether as eluent) to yieldthe product.
95% With potassium carbonate In ethanol; water monomer at 20℃; for 20h;
95% With potassium carbonate In water monomer; N,N-dimethyl-formamide at 100℃; for 0.333333h; Microwave irradiation;
95% With potassium carbonate In water monomer; isopropanol at 28℃; for 3h;
95% With potassium carbonate In water monomer; isopropanol at 28℃; for 3h;
95% With C17H18N2O6PdS; potassium carbonate In water monomer at 20℃; for 5h;
94% With potassium carbonate In 5,5-dimethyl-1,3-cyclohexadiene at 90℃; for 6h; Inert atmosphere;
94% With potassium carbonate In water monomer; isopropanol at 60℃; for 6h; 2.5 General procedure for the Suzuki-Miyaura reactions of aryl halides using Pd-catalyst General procedure: A 50 ml round bottomed flask was charged with a mixture of aryl halide (1 mmol), arylboronic acid (1.1 mmol), K2CO3 (3 mmol), catalyst (appropriate quantity), solvent (6 ml). The mixture was refluxed under stirring condition at 60 °C for the required time. After completion, the catalyst was separated by filtration and the residual solid was washed with the same reaction solvent for several times. The filtrate was diluted with water (20 ml) and extracted with ether (3× 20 ml). The combined extract was washed with brine (3× 20 ml) and dried over Na2SO4. After evaporation of the solvent under reduced pressure, the residue was chromatographed (silica gel, ethyl acetate/hexane, 1:9) to obtain the desired products. For recycling experiments, after each cycle of utilization, the catalyst was washed several times under refluxing conditions with iPrOH/H2O followed by DCM to remove any occluded reactants and products physically attached with the catalyst surface. After drying the recovered catalyst at 120 °C overnight, transferred it to a reaction vessel containing substrates, base and solvent and performed the reactions under identical conditions.
94% With C21H20N2O2Pd; potassium carbonate In water monomer; isopropanol at 25℃; for 0.5h; General procedure for Suzuki Miyaura reaction General procedure: A 25 mL synthesiser tube had taken with a mixture of aryl halide (0.5 mmol), aryl boronic acid (0.55 mmol), base (1.5 mmol), Pd complex C1 (0.2 mol %) and the mixture was stirred in 2 mL of aqueous isoproponol (1:1) at room temperature for the required time. After completion, the reaction mixture was extracted with ether (3 × 20 mL). The combined extract was washed with brine (2 × 20 mL) and dried over Na2SO4. After evaporation of the solvent under reduced pressure, the residue was chromatographed (silica gel, ethyl acetate-hexane: 1:9) to obtain the desired products.The products were confirmed by comparing the 1H and 13C NMR and mass spectral data with authentic samples.
94% With sodium phosphate tribasic dodecahydrate In ethanol; water monomer at 20℃; for 4h;
94% With C37H37AsClNPd; potassium carbonate In ethanol at 70℃; for 6h;
94% With potassium carbonate In water monomer; isopropanol at 28℃; for 3.5h; 5.5 Standard Procedure for Suzuki-Miyaura Reaction General procedure: A 50 ml round-bottom flask was charged with a mixture of aryl halide (0.5 mmol), arylboronic acid (0.55 mmol), K2CO3 (1 mmol), catalyst (10 mg, 0.22 mol% Pd) and i-PrOH/H2O (4 mL). The mixture was stirred at room temperature for the indicated time. After completion, the reaction mixture was subjected to centrifugation followed by filtration and the residual solid was washed with the same solvent (3 X 5 mL). The resultant filtrate was diluted with brine (10 mL) and extracted with diethyl ether (3 9 mL), dried over anhydrous Na2SO4, and evaporated under reduced pressure. The crude residue was subjected to silica gel column chromatography (ethyl acetate-hexane, 0.5: 9.5) to obtain the desired products.
93% With palladium diacetate; potassium carbonate In tetrahydrofuran; water monomer for 10h; Inert atmosphere; Reflux;
93% With tripotassium phosphate tribasic; tetrabutylammonium bromide In water monomer at 75℃; for 0.6h; Ionic liquid;
93% With tripotassium phosphate tribasic; tetrabutylammonium bromide In water monomer at 65℃; for 0.5h;
93% With 2Na(1+)*C26H18N2O8PdS2(2-); potassium carbonate In water monomer at 20℃; for 10h; General procedure: The Suzuki reaction was performed in a 50 mL round-bottomed flask, aryl halide (0.5 mmol), arylboronic acid (0.65 mmol), K2CO3 (1 mmol), Complex 1 (0.2-1 mol%) and water (4 mL) were charged and stirred for the required time at room temperature for aryl bromides or at 100 °C for aryl chlorides. After completion, the mixture was cooled down to room temperature, diluted with water (10 mL) and extracted with diethyl ether (3 × 15 mL). The organic layer was washed with brine (3 × 15 mL), dried over anhydrous Na2SO4. The crude products were chromatographed on silica gel (ethyl acetate/hexane).
93% With potassium carbonate In water monomer at 50℃; for 0.5h;
93% With dicyclohexyl({2’,6’-dimethoxy-[1,1‘-biphenyl]-2-yl})phosphane; copper (I) iodide In ethanol at 80℃; for 4.5h;
92% With potassium hydroxide; C13H16NO4S(1-)*Na(1+); palladium (II) chloride In water monomer at 100℃; for 3h;
92% With C26H26N4O8Pd2; potassium carbonate In water monomer at 20℃; for 24h; General procedure for the Suzuki-Miyaura reaction General procedure: A 50 ml round bottom flask was charged with a mixture of aryl halide (0.5 mmol), arylboronic acid (0.55 mmol), K2CO3 (1.5 mmol), and Pd catalyst (0.2 mol% for aryl bromide or 1 mol% for aryl chloride) and the mixture was stirred for required times at room temperature in water (6 ml) for aryl bromides/at 80 °C in aqueous-glycerol (6 ml) for aryl chlorides. After completion, the reaction mixture was diluted with water (20 ml) and extracted with ether (20 ml × 3). The combined extract was washed with brine (20 ml × 3) and dried over Na2SO4. After evaporation of the solvent under reduced pressure, the residue was chromatographed (silica gel, ethyl acetate/hexane 1:9) to obtain the desired product. The products were confirmed by comparing the 1H NMR and mass spectral data with authentic samples.
92% With C21H15ClN2O2Pd; potassium carbonate In water monomer at 50℃; for 1h; General procedure for Suzuki Miyaura reaction General procedure: A 25 mL synthesizer tube was taken with a mixture of aryl halide (0.5 mmol), aryl boronic acid (0.55 mmol),base (1.5 mmol), Pd-complex C1 (0.2 mol %) and the mixture was stirred in2 mL of water at 50°C for the required time. After completion, the reaction mixture was extracted with ether (3 Χ 20 mL). The combined extract was washed with brine (2 Χ 20 mL) and dried over Na2SO4. After evaporation of the solvent under reduced pressure, the residue was chromatographed (silica gel,ethyl acetate-hexane: 1:9) to obtain the desired products. The products were confirmed by comparing the 1H and 13C NMR and mass spectral data with authentic samples.
92% With water extract of waste papaya bark ash; palladium diacetate In ethanol at 28℃; for 0.5h; Green chemistry;
92% With potassium carbonate In 5,5-dimethyl-1,3-cyclohexadiene at 60℃; for 8h; Suzuki reaction of aryl bromides with arylboronic acids; general procedure General procedure: A mixture of aryl bromide (1.0 mmol), arylboronic acid (1.5 mmol),potassium carbonate (2.0 mmol), xylene (3 mL) and the MCM-41-2N,S-Pd(0) complex (13 mg, 0.005 mmol of Pd) was stirred at 60 °Cunder air for 3-12 h. The mixture was cooled and the MCM-41-2N,SPd(0) complex was filtered off. It was then washed with distilled water(2 × 10 mL), EtOH (2 × 10 mL) and Et2O (2 × 10 mL). The filtrate waspoured into a saturated aqueous NaCl solution (50 mL) and extractedwith CH2Cl2 (2 × 50 mL). The extracts were washed with water(3 × 20 mL) and dried over MgSO4. After removal of the solvent, theresidue was purified by column chromatography on silica gel usinghexane or hexane/ethyl acetate (15:1 to 20:1) as eluent.
92% With Pd-BaSO4 at 100℃; for 2h; 13 Example 13: Preparation of 4-methoxy-4'-chlorobiphenyl Add 4-bromoanisole (1mmol), 4-chlorophenylboronic acid (1.1mmol) and palladium barium sulfate catalyst (0.001mmol), and Suaeda extract (4ml) to a 10ml round bottom flask at 100°C in air Stir for 2 hours. After the reaction, the mixture was cooled to room temperature. After filtration, the obtained filter residue was mixed with a palladium catalyst to obtain a mixture dissolved in 20 mL of ethyl acetate. After filtration, the solution was collected, and the final product was obtained after evaporation to dryness. The product structure was identified by nuclear magnetic resonance hydrogen spectrum and carbon spectrum. The yield was 92%.
92% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); tripotassium phosphate tribasic; (2′-(bicyclo[2.2.1]heptan-2-yl)-[1,1′-biphenyl]-2-yl)diphenylphosphane In tetrahydrofuran; water monomer at 100℃; for 10h; Inert atmosphere; Schlenk technique;
91% With potassium carbonate In ethanol; water monomer at 30℃; for 12h;
91% With potassium carbonate In ethanol; water monomer at 20℃; for 0.5h;
90% With potassium carbonate In ethanol at 78℃; for 1h; Air atmosphere;
90% With 1-phenylethanone-O-(4-chloro-phenyl)oxime; tetrabutylammonium bromide; potassium carbonate; palladium (II) chloride In water monomer at 27℃; for 4h; Green chemistry; Typical experimental procedure for Suzuki-Miyaura reaction of aryl bromideswith aryl boronic acids General procedure: All the reactions were carried out in open atmosphere. A mixture of arylbromide (0.5 mmol), aryl boronic acid (0.55 mmol), K2CO3 (1 mmol), PdCl2(1 mol %), ligand (2 mol %), TBAB (0.5 mmol), and water (4 mL) was stirred atroom temperature for the indicated time in a 25 mL round bottom flask. Theprogress of the reaction was monitored using TLC (Merck silica gel 60F254plates) under UV light. After completion, the reaction mixture was diluted withbrine (10 mL) and extracted with ether (3 10 mL). The combined extract wasdried over anhydrous Na2SO4. After evaporation of ether under vacuum, theproduct was isolated by short-chromatography {silica gel (60-120 mesh), ethylacetate-hexane; 0.5:9.5}. The isolated products were confirmed by comparingtheir 1H and 13C NMR and mass spectral data with reported samples
90% With anhydrous sodium carbonate In ethanol; water monomer at 20℃; for 8h; Inert atmosphere;
90% With bis(acetonitrile)palladium(II) chloride; C95H120N20O10(10+)*10F6P(1-); potassium carbonate In ethanol at 50℃; for 1.5h; General procedure for the Suzuki coupling reactions General procedure: In a typical run, a mixture of aryl bromide (0.50 mmol),phenylboronic acid (0.55 mmol), K2CO3 (1.5 mmol),0.2 mol% ligand, 1 mol% PdCl2(CH3CN)2 in 1.5 mL of ethanol were stirred at 50 C for 1.5 h under air. Solvent ethanol was removed completely under vacuum degree0.09 MPa at 45 C to give a crude product. The pure product was isolated by column chromatography on silica.
90% With bis(((1Z,3Z)-3-((1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)imino)-1,3-diphenylprop-1-en-1-yl)oxy)palladium; potassium carbonate In water monomer; N,N-dimethyl-formamide at 80℃; for 4.5h; General procedure for the Heck-Mizoroki reaction General procedure: A mixture of aryl halide (1mmol), olefin (1mmol), K2CO3 (1mmol), and the Pd-Schiff base complex (2.1mg, 0.2mol %) in DMF-H2O (1:1) was stirred at 80°C for 3-4h. The reaction progress was monitored periodically by TLC. After completion of the reaction, it was cooled to room temperature and the product was extracted with ethyl acetate (3×10mL) from aqueous phase. The combined organic fractions were dried over Na2SO4, the solvent removed under reduced pressure to afford a crude product. The residue was purified by short column chromatography on silica gel eluted with petroleum ether/ethyl acetate afforded the desired coupled products up to 98% yield. The products were confirmed by 1H and 13C NMR.General procedure for the Suzuki-Miyaura reaction: A mixture of aryl halide (1mmol), arylboronic acid (1mmol), K2CO3 (1mmol), and the Pd- Schiff base complex (2.1mg, 0.2mol %) in DMF-H2O (1:1) was stirred at 80°C for 3-5h. The progress of reaction was monitored by TLC until the complete consumption of the aryl halide. After the reaction, the mixture was cooled down to room temperature and repeatedly extracted with ethyl acetate. The combined organic layer was separated, dried over Na2SO4 and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel to give the corresponding coupling products in up to 95% isolated yield. The products were confirmed by 1H and 13C NMR.
90% With chloro-2,6-bis((sec-butylthio)methyl)pyridinepalladium(II) chloride; tetrabutylammonium bromide; potassium hydroxide In water monomer at 120℃; for 1.5h; Inert atmosphere; Schlenk technique; Sealed tube; General Suzuki-Miyaura cross-coupling procedure General procedure: A 50-mL Schlenk tube was charged with aryl halide (1.63 mmol), aryl boronic acid (2.61 mmol), KOH (3.26 mmol), complex 17d (0.5 mol %), TBAB (0.5 mol % relative to the aryl halide) and water (2 mL). The sealed mixture was stirred at 120 °C until TLC analysis confirmed completion of the reaction (for GC analysis the products were extracted with toluene). The aqueous solution was then extracted with ethyl acetate (3 10 mL). The combined organic phases were dried over MgSO4, filtered and evaporated in vacuo. The residue product was purified by column chromatography on silica gel using a mixture of hexane and ethyl acetate as eluent to yield biaryls 23a-m:
88% With potassium carbonate In ethanol; water monomer at 65℃; for 8h;
88% With potassium carbonate In ethanol; water monomer at 60℃; for 24h;
88% With potassium carbonate In water monomer at 20℃; for 7h; Suzuki-Miyaura cross-coupling reaction General procedure: For Suzuki-Miyaura reaction, appropriate amount of the catalyst, PdNP-NMe2SiO2, was added to a mixture of aryl halide (0.5 mmol), arylboronic acid (0.65 mmol), K2CO3 (1.5 mmol) in 6 mL solvent. The reaction was then stirred under desired temperature for the required time. The initial progress of the reaction was monitored by TLC using aluminum coated TLC plates (Merck) under UV light and the product formation was determined using GC-MS. After completion, the catalyst was collected by filtration and washed with isopropanol-water. The filtrate was diluted with water and extracted with ether and then dried over Na2SO4. After evaporation of the solvent under reduced pressure, the residue was chromatographed (silica gel, ethyl acetate-hexane, 1:9) to obtain the desired product.
87% With C17H23Br2N3Pd; potassium-t-butoxide In water monomer at 20℃; for 24h; Inert atmosphere; 2.2. General procedure for the Pd(II)-NHC complex 1-catalyzed Suzuki-Miyaura cross-coupling reaction of arylboronic acids with aryl iodides and bromides General procedure: (If aryl halide is a liquid) under N2 atmosphere, arylboronic acid 3 (0.6 mmol), Pd(II)-NHC 1 (1.0 mol%), KOBut (1.0 mmol) and H2O (2.0 mL) were added into a Schlenk tube, then aryl halide 2 (0.5 mmol) was added. The mixture was stirred vigorously at room temperature for 24 h. Then the solventwas removed under reducedpressure and the residue was purified by a flash column chromatography (SiO2) to give the pure product.(If aryl halide is a solid) under N2 atmosphere, aryl halide 2 (0.5 mmol), arylboronic acid 3 (0.6 mmol), Pd(II)-NHC 1 (1.0 mol%), KOBut (1.0 mmol) and H2O (2.0 mL) were added into a Schlenk reaction tube. The mixture was stirred vigorously at room temperature for 24 h. Then the solventwas removed under reduced pressure and the residue was purified by a flash column chromatography (SiO2) to give the pure product.
87% With [Pd(Cl)κ2-S,N-C6H4CS=N-(4-Py)(PPh3)]; potassium carbonate In toluene at 80℃; for 5h;
86% With C30H24ClN2OPPdS; potassium carbonate In water monomer at 100℃; for 3h;
83% With C12H12Cl2N4O2Pd; Cs2CO3 In water monomer at 60℃; for 4h; General procedure for the Reaction of Arylboronic Acids and Halobenzenes General procedure: In an oven dried 10 mL round bottom flask were added arylboronic acid 1 (1.0 mmol), halobenzene 2 (1.0 mmol), Cs2CO3 (0.5 equiv) and catalyst C4 (1.0 mol%) in water (1mL). The reaction mixture was allowed to stir at 60 oC for completion. After completion of reaction (monitored by TLC) the crude residue was extracted into in ethylacetate (10 mL x 3) and dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure. The crude mixture was separated using silica-gel column chromatography by eluting with ethylacetate/hexanes.
82% With sodium hydroxide In water monomer at 100℃; for 6h;
80% With 3,5-di-tert-butyl-2-hydroxybenzaldehyde; potassium carbonate; palladium (II) chloride In ethanol; water monomer at 20℃; for 2h; General procedure for Suzuki-Miyaura reaction General procedure: To a round bottle with a magnetic stir bar, ligand (0.01% mmol), PdCl2 (0.01% mmol), aryl halides (1.0 mmol), phenylboronic acid (1.2 mmol), K2CO3 (2.0 mmol) and 6 ml of solvent were added. The reaction mixture was conducted at room temperature for the required time, and then the solvent was removed under reduced pressure. The residual was diluted with Et2O (5 mL), followed by extraction twice (2×5 mL) with Et2O. The organic layer was dried with anhydrous MgSO4, filtered and evaporated under vacuum. The conversions rates were analyzed by gas chromatography, based on the peak area normalization method. The corrected factor was determined by samples against a standard of n-heptane. The crude products were purified by silica-gel column chromatography using petroleum ether-ethyl acetate (20:1) as an eluent, and the isolated yield was then calculated based on the feeding of the aryl halide. The isolated corresponding products were characterized by 1H NMR and 13C NMR.
78% With potassium carbonate In ethanol; water monomer at 20℃; Green chemistry;
78% With C21H19N2(1+)*Br(1-); palladium diacetate; potassium carbonate In toluene at 70℃; for 3h; 3. Catalytic Coupling ReactionsGeneral procedure for Palladium(II)-catalyzed Suzuki-Miyaura reaction: General procedure: A reaction tube was charged with Pd(OAc)2 (1.34 mg, 0.006 mmol), imidazolium salt (0.0072 mmol), K2CO3 (62 mg, 0.45 mmol), and ArB(OH)2 (0.45 mmol). To the reaction tube were added toluene (2.0 mL) and aryl bromide (0.3 mmol). The mixture was stirred at 70 °C in the presence of air for 3 hours. The mixture was cooled to room temperature and directly purified through silica gel column chromatography to give the product.
75% With 2,2'-diamino-6,6'-dimethylbiphenyl; palladium diacetate; Cs2CO3 In tetrahydrofuran at 70℃; for 24h; Inert atmosphere;
74% With tert-butyldicyclohexylphosphine; palladium diacetate; anhydrous sodium carbonate In cyclohexane; water monomer at 100℃; for 5h; Sealed tube; Inert atmosphere;
70% With (3aS,7aS)-1,3-di-o-tolyl-octahydro-benzoimidazole-2-thione; potassium carbonate In water monomer; isopropanol at 80℃; for 5h;
64% With C26H18Cl2N6NiO2; potassium carbonate In toluene for 8h; Reflux; Typical procedure for the Suzuki-Miyaura reactions General procedure: (1.0 mmol) and K2CO3 (2.0 mmol) in toluene (10 mL),1(0.5 mol%) were added. The resultant mixture was refluxed for 8 h, there action mixture was then cooled to room temperature, H2O(10 mL) added and the organic layer was extracted with EtOAc(3x20 mL). The solvent was stripped off and the remaining residue was purified by column chromatography (n-hexane-EtOAc) to yield the pure product. The products were confirmed by 1H NMR. For the double cross-coupling reaction the procedure was similar to that mentioned above where dibromide (1.0 mmol),arylboronic acid (2.0 mmol), 1 (1.0 mol%) and K2CO3 (4.0 mmol) in toluene (10 mL) were used.
38% With dicyclohexyl({2’,6’-dimethoxy-[1,1‘-biphenyl]-2-yl})phosphane; palladium diacetate; potassium carbonate In 1,4-dioxane; water monomer at 100℃; for 1h; Inert atmosphere;
75 % Chromat. With tetrabutylammonium bromide; potassium carbonate at 120℃; for 0.333333h; microwave irradiation;
90 % Chromat. With potassium carbonate In water monomer; N,N-dimethyl-formamide at 100℃; for 0.16h; microwave irradiation;
With C33H27BrN3O3PPd; potassium carbonate In methanol at 70℃; for 6h; 4.4. General procedure for Suzuki-Miyaura coupling reactions General procedure: In a typical run, an oven dried 25 mL flask equipped with a stir bar was charged with a known catalyst (0.001 mmol), base (1.5 mmol) and phenylboronic acid (0.75 mmol). To the above mixture methanol (5 mL) and aryl halide (0.5 mmol) were added. The reactions were allowed to reflux at 70 °C. After the specified time the flask was removed from the oil bath. The solvent was removed and water (10 mL) was added followed by extraction with diethyl ether (3 × 10 mL) and the catalyst was regenerated. The combined organic layers were washed with water (3 × 10 mL), dried over anhydrous Na2SO4, and filtered. The organic layers were evaporated under reduced pressure and the residue was analyzed by 1H NMR. All the conversions were taken from 1H NMR spectroscopy based on arylbromide methyl group [57] and [58] and the 1H NMR data of all the products were given in supporting information.
94 %Chromat. With C16H36N(1+)*C19H23Cl2N2O3PdS(1-); water monomer; potassium carbonate for 0.0833333h; Microwave irradiation;
With C33H29N4O2PPdS; potassium carbonate Reflux;
91.1 %Chromat. With potassium carbonate In water monomer at 80℃; for 1h; Green chemistry;

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  • 11
  • [ 874148-10-4 ]
  • potassium 4-(methoxy)phenyltrifluoroborate [ No CAS ]
  • [ 58970-19-7 ]
YieldReaction ConditionsOperation in experiment
75% With tetrakis(triphenylphosphine) palladium(0); triethylamine; silver(l) oxide In methanol for 1.5h; Heating;
  • 12
  • [ 106-39-8 ]
  • [ 5720-07-0 ]
  • [ 58970-19-7 ]
YieldReaction ConditionsOperation in experiment
95% With sodium carbonate; In ethanol; water; at 120℃; for 0.0833333h;Sealed tube; Microwave irradiation; Green chemistry; General procedure: Into a 10 mL glass vial were placed aryl halide (0.5 mmol), phenyl- or4-methoxy phenylboronic acid (0.65 mmol), base (1 mmol), Pd-loadedcatalyst 4 (0.2 mol% Pd) and EtOH/water (1 : 1) (2 mL), and a magneticstirrer was added. The vial was sealed, placed into the microwavecavity and the reaction mixture subjected to microwave irradiation of60 W at 120 C for 5 min. After completion, the reaction vessel wascooled to room temperature, opened and the contents were extractedwith dichloromethane three times. The organic fraction was dried withmagnesium sulfate, filtered and the solvent was removed under reducedpressure. The crude products were purified by chromatography on asilica gel column. All products were identified by 1H NMR.
94% With 2C60H80NaO12*Cl6Pd2; potassium carbonate; In methanol; water; at 20℃; for 0.166667h; General procedure: A mixture of aryl bromides (0.5 mmol), aryl boronic acid (0.6 mmol), K2CO3 (0.6 mmol), catalyst 2 (0.2 mol%), and CH3OH/H2O (2/1, 2 mL) was stirred at room temperature under air. The reaction mixture was stirred for 10 min, and then diluted with water and CH2Cl2. The organic layer was separated and the aqueous layer was extracted with CH2Cl2 for three times. The combined organic phase was dried with MgSO4, filtrate, solvent was removed on a rotary evaporator, and the product was isolated by thin layer chromatography. The purified products were identified by 1H NMR, 13C NMR spectroscopy and melting points with the literature data.
94% With potassium carbonate; In ethanol; water; at 25℃; for 3h; General procedure: In a thermostatted bath at 25C (or 60C for compounds 18 and 28), a 25 mL Schlenk flask was charged in air with a magnetic stir bar, arylbromide (0.5 mmol), arylboronic acid (0.6 mmol), K2CO3 (0.6 mmol), 1 (26.6 mg, 1mol-%), ethanol (1.5 mL), and water (0.5 mL). The reaction mixture was kept under vigorous stirring until the GC control showed no residual aryl bromide in solution. Water (10 mL) was added to the suspension and the organics were extracted with dichloromethane (3×10 mL). The solution was dried over Na2SO4 and then passed through a column filled with silica gel (diatomaceous earths were used in the case of compound 28). Elimination of the solvent under vacuum gave the desired biaryl as white microcrystalline solid. Purity (96÷99%) was established by GC and 1H NMR. 1H and 13C{1H} NMR data of compounds 8-28. Spin multiplicity is given by s=singlet, br s=broad singlet, q=quartet, st=septet, qq=quartet of quartets, ddd=doublet of doublets of doublets, m=unresolved multiplet. 4-Chloro-4'-methoxy-1,1'-biphenyl (17). Yield 94%. C13H11OCl (218.68): calcd. C 71.40, H 5.07; found C 71.27, H 5.13. 1H NMR (CDCl3): delta = 7.58-7.44 (4H, m), 7.42-7.33 (2H, m), 7.08-6.95 (2H, m), 3.86 (3H, s, OCH3) ppm. 13C NMR (CDCl3): delta = 159.3, 139.2, 132.6, 132.4, 128.8, 128.0, 127.9, 114.3, 55.3 (OCH3) ppm.
89% With potassium carbonate; In ethanol; water; at 50℃; for 1h; General procedure: A flame-dried 50mL round-bottom flask equipped with amagnetic stir bar and a rubber septum was charged with arylhalide (1.0mmol), phenyl boronic acid (1.1mmol), K2CO3(2.0mmol) and CL-salen-Pd(II) (0.5% mmol). The mixturewas stirred in Ethanol: H2O= 1:1 (5.0mL) at 50 underair atmosphere for 1h. The mixture was cooled to roomtemperature, quenched with water (5mL), and diluted withethyl acetate (5mL). The layers were separated, and theaqueous layer was extracted with 2 × 5mL of ethyl acetate.The combined organic extracts were dried over anhydrousmagnesium sulfate, filtered, and concentrated in vacuo.Finally, the product was purified by column chromatography.
78% With C21H19N2(1+)*Br(1-); palladium diacetate; potassium carbonate; In toluene; at 70℃; for 3h; General procedure: A reaction tube was charged with Pd(OAc)2 (1.34 mg, 0.006 mmol), imidazolium salt (0.0072 mmol), K2CO3 (62 mg, 0.45 mmol), and ArB(OH)2 (0.45 mmol). To the reaction tube were added toluene (2.0 mL) and aryl bromide (0.3 mmol). The mixture was stirred at 70 C in the presence of air for 3 hours. The mixture was cooled to room temperature and directly purified through silica gel column chromatography to give the product.

  • 13
  • C13H11ClN4O3 [ No CAS ]
  • [ 5720-07-0 ]
  • [ 58970-19-7 ]
  • [ 97-52-9 ]
YieldReaction ConditionsOperation in experiment
With boron trifluoride diethyl etherate In methanol at 20℃; for 3h;
  • 14
  • [ 599-89-3 ]
  • [ 13139-86-1 ]
  • [ 58970-19-7 ]
YieldReaction ConditionsOperation in experiment
88% With PinP(O)H In tetrahydrofuran; 1,4-dioxane at 80℃; for 22h;
  • 15
  • [ 17151-48-3 ]
  • p-methoxybenzenediazonium o-benzenedisulfonimide [ No CAS ]
  • [ 58970-19-7 ]
YieldReaction ConditionsOperation in experiment
87% In tetrahydrofuran at 20℃; for 1.75h;
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