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[ CAS No. 591-50-4 ]

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Chemical Structure| 591-50-4
Chemical Structure| 591-50-4
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CAS No. :591-50-4 MDL No. :MFCD00001029
Formula : C6H5I Boiling Point : 188°C at 760 mmHg
Linear Structure Formula :- InChI Key :-
M.W :204.01 g/mol Pubchem ID :11575
Synonyms :

Safety of [ 591-50-4 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P305+P351+P338 UN#:N/A
Hazard Statements:H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 591-50-4 ]

  • Upstream synthesis route of [ 591-50-4 ]
  • Downstream synthetic route of [ 591-50-4 ]

[ 591-50-4 ] Synthesis Path-Upstream   1~34

  • 1
  • [ 288-88-0 ]
  • [ 591-50-4 ]
  • [ 13423-60-4 ]
YieldReaction ConditionsOperation in experiment
96% With potassium phosphate; copper(l) iodide; N,N`-dimethylethylenediamine In N,N-dimethyl-formamide at 110℃; for 72 h; Inert atmosphere General procedure: A mixture of CuI (0.10 g, 0.50 mmol), the required azole(10 mmol), K3PO4 (4.4 g, 20 mmol), the required halide (12 mmol)and N,N0-dimethylethylenediamine (0.11 mL, 1.0 mmol) in DMF(5 mL) was degased and heated under argon at 110 C for 72 h.After filtration over celite (washing using AcOEt) and removal ofthe solvents, the crude product is purified by chromatography oversilica gel (the eluent is given in the product description). 4.3.1
1-Phenyl-1H-1,2,4-triazole (2a)
Compound 2a was prepared from 1,2,4-triazole (0.69 g) and iodobenzene (1.4 mL) using the general procedure 1, and was isolated (eluent: heptane/AcOEt 7:3) in 96percent yield as a yellow powder: mp 48 °C (lit.
28
46 °C); 1H NMR (CDCl3, 300 MHz) 7.42 (m, 1H), 7.53 (m, 2H), 7.71 (m, 2H), 8.15 (s, 1H), 8.74 (s, 1H); 13C NMR (CDCl3, 75 MHz) 120.1 (2CH), 128.3 (CH), 129.9 (2CH), 137.1 (C), 140.9 (CH), 152.7 (CH).
91% With caesium carbonate In DMF (N,N-dimethyl-formamide) at 50 - 82℃; for 24 - 72 h; Example 1.17 [0636] Preparation of 1-phenyl-1H-1,2,41 triazole [0637] Operating protocol A (82 C., 48 hours) was followed using 117 mg of Chxn-Py-Al (0.4 mmoles), 336 ?l of iodobenzene (3 mmoles), 138 mg of 1,2,4-triazole (2 mmoles), 1.042 g of caesium carbonate (3.2 mmoles) and 1.2 ml of DMF. [0638] The degree of transformation and selectivity were 100percent and 98percent respectively. [0639] The residue obtained following treatment was purified by silica gel chromatography (eluent: hexane/dichloromethane, 100/0 to 50/50). [0640] 264 mg of a dark yellow solid was obtained in a yield of 91percent. [0641] Pale yellow needles were obtained after re-crystallisation from chloroform. [0642] The compound obtained had the following formula: [CHEMMOL-00056] [0643] The characteristics were as follows: [0644] MPt: 46 C. (CHCl3) (Lit: 46-47 C. given by Micetich, R G; Spevak, P; Hall, T W; Bains, B K; Heterocycles 1985, 23, 1645-1649); [0645] H NMR/CDCl3:? 8.52 (wide s, 1H, HI), 8.04 (wide s, 1H, H2), 7.53-7.65 (m, 2H, H4,8), 7.26-7.51 (m, 3H, H5,6,7); [0646] 13C NMR/CDCl3: ? 152.55 (C1), 140.88 (C2), 139.96 (C3), 129.73 (C5 and C7), 128.15 (C6), 119.99 (C4 and C8); [0647] GC/MS: Rt=14.02 min, M/Z=145, purity=100percent; [0648] Rf=0.21 (eluent: dichloromethane/ethyl acetate, 90/10). Example 1.18 [0649] Preparation of 1-phenyl-1H-[1,2,4]triazole [0650] Operating protocol A (82 C., 24 hours) was followed using 117 mg of Chxn-Py-Al (0.4 mmoles), 336 ?l of iodobenzene (3 mmoles), 138 mg of 1,2,4-triazole (2 mmoles), 1.042 g of caesium carbonate (3.2 mmoles) and 1.2 ml of DMF. [0651] The degree of transformation and selectivity were 79percent and 99percent respectively. [CHEMMOL-00057] Example 1.19 [0652] Preparation of 1-phenyl-1H-[1,2,4]triazole Example 1.18 was repeated, operating at 50 C. (72 hours). The degree of transformation and selectivity for 1-phenyl-1H-[1,2,4-triazole] were 75percent and 99percent respectively. [0653] [CHEMMOL-00058]
91%
Stage #1: at 100℃;
Stage #2: at 50 - 82℃; for 24 - 72 h;
Operating protocol A (82° C., 48 hours) was followed using 117 mg of Chxn-Py-Al (0.4 mmoles), 336 μl of iodobenzene (3 mmoles), 138 mg of 1,2,4-triazole (2 mmoles), 1.042 g of caesium carbonate (3.2 mmoles) and 1.2 ml of DMF. The degree of transformation and selectivity were 100percent and 98percent respectively. The residue obtained following treatment was purified by silica gel chromatography (eluent: hexane/dichloromethane, 100/0 to 50/50). 264 mg of a dark yellow solid was obtained in a yield of 91percent. Pale yellow needles were obtained after re-crystallisation from chloroform. The compound obtained had the following formula: The characteristics were as follows: MPt: 46° C. (CHCl3) (Lit: 46-47° C. given by Micetich, R G; Spevak, P; Hall, T W; Bains, B K; Heterocycles 1985, 23, 1645-1649); 1H NMR/CDCl3: δ8.52 (wide s, 1H, H1), 8.04 (wide s, 1H, H2), 7.53-7.65 (m, 2H, H4,8), 7.26-7.51 (m, 3H, H5,6,7); 13C NMR/CDCl3: δ 152.55 (C1), 140.88 (C2), 139.96 (C3), 129.73 (C5 and C7), 128.15 (C6), 119.99 (C4 and C8); GC/MS: Rt=14.02 min, M/Z=145, purity=100percent; Rf=0.21 (eluent: dichloromethane/ethyl acetate, 90/10). Example 1.18; Preparation of 1-phenyl-1H-[1,2,4]triazole; Operating protocol A (82° C., 24 hours) was followed using 117 mg of Chxn-Py-Al (0.4 mmoles), 336 μl of iodobenzene (3 mmoles), 138 mg of 1,2,4-triazole (2 mmoles), 1.042 g of caesium carbonate (3.2 mmoles) and 1.2 ml of DMF. The degree of transformation and selectivity were 79percent and 99percent respectively. ; Example 1.19; Preparation of 1-phenyl-1H-[1,2,4]triazole; Example 1.18 was repeated, operating at 50° C. (72 hours). The degree of transformation and selectivity for 1-phenyl-1H-[1,2,4-triazole] were 75percent and 99percent respectively.
83% With caesium carbonate In N,N-dimethyl-formamide at 90℃; for 30 h; sealed tube Preparation of 1-phenyl-1H-[1,2,4]triazole [0220] Following General Procedure A (90 0C, 30 hours), 1/-/-[1 ,2,4]triazole (104 mg, 1.5 mmol) is coupled with iodo-benzene (112 μL, 1.0 mmol). The crude brown oil is purified by flash chromatography on silica gel (eluent: dichloromethane/hexanes = 50/50) to provide 120 mg (83 percent isolated yield) of the desired product as a light yellow solid. <n="50"/>007/001836_ 49 -IdentificationMp: 460C.1H NMR (400 MHz, CDCI3): δ 8.49 (s, 1 H1 H8), 8.03 (s, 1H, H7), 7.58-7.61 (m, 2H, H2i6), 7.40-7.44 (t, 2H1 H3,5), 7.31-7.33 (t, 1 H, H4).13C NMR (100 MHz, CDCI3): δ 152.62 (C7), 140.91 (C8), 136.99 (C1), 129.77 (C3,5), 128.21 (C4), 120.04 (C2i6).IR (KBr) : v (cm'1) = 3105, 2924, 2852, 1600, 1514, 1416, 1359, 1278, 1223,1152, 1055, 981 , 876, 754, 681 , 671 , 503.GC/MS: rt = 15.28 min, M/Z = 145.HRMS: 146.0721 (M+H). Theoretical: 146.0718
71%
Stage #1: Inert atmosphere
Stage #2: at 120℃; for 64 h; Inert atmosphere
A flask was charged with K2CO3 (12.1689 g, 88 mmol), 1H-1,2,4-triazole (2.0042 g, 29 mmol), Cu2O(430 mg, 3 mmol) and 1,10-phenanthroline (1.0452 g, 5.8 mmol) and then evacuated and back-filled with N2. Then, anhydrous DMF (20 ml) and iodobenzene (8.9764 g, 4.92 ml, 44 mmol) were added and the resulting mixture was heated to 120 °C for 64 h and then diluted with CH2Cl2 (40 ml). The mixture was filtered through a pad of Celite and the residue washed with CH2Cl2 (20 ml). The resulting organic layer was washed with water (20 ml) and brine (20 ml), dried over MgSO4 and concentrated under reduced pressure. The crude mixture was purified by column chromatography (cyclohexane/ethyl acetate 8/0→2/0) to yield the product as a pale yellow solid (2.986 g, 71percent).
65%
Stage #1: With phenanthroline monohydrate; potassium carbonate In N,N-dimethyl-formamideInert atmosphere
Stage #2: at 100℃; for 48 h;
EXAMPLE 108
1-phenyltriazole 1 g (0.0145 mol) triazole 2, 0.21 g (0.00145 mol) copper(I)oxide, 0.29 g (0.00145 mol) phenantroline monohydrate and 6.01 g (0.044 mol) potassium carbonate are weighed into a Schlenk flask. After repeated evacuating and flushing with argon, 10 ml dry DMF is added. Evacuating and flushing with argon are repeated several times. Subsequently, 2.42 ml (4.43 g, 0.022 mol) of iodobenzene is added. The reaction mixture is stirred for 48 h at 100° C. under argon. After cooling 20 ml DCM is added and filtered. The solvent is removed in vacuum and the product is obtained after purification by column chromatography (KG 60, gradient petroleum ether/EtOAc 8:2 to EtOAc) as a yellowish-white solid.M 145.17 C8H7N3 Yield: 1.362 g (65percent)1H-NMR DM-94 (300 MHz/DMSO): (ppm)=7.41 (t, 1H, 6-H); 7.58 (t, 2H, 5/5'-H); 7.87 (d, 2H, 4-H); 8.25 (s, 1H, 1-H); 9.31 (s, 1H, 2-H)13C-NMR DM-94 (75.475 MHz/DMSO): (ppm)=119.37 (5/5'-C); 127.78 (6-C); 129.77 (4/4'-C); 136.74 (3-C); 142.27 (2-C); 152.39 (1-C)

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[2] Journal of Organic Chemistry, 2007, vol. 72, # 8, p. 2737 - 2743
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[9] Patent: US2003/236413, 2003, A1, . Location in patent: Page 24-25
[10] Patent: US2005/234239, 2005, A1, . Location in patent: Page/Page column 23; 28-29
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[15] Patent: WO2008/4088, 2008, A2, . Location in patent: Page/Page column 48-49
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[24] Tetrahedron Letters, 2007, vol. 48, # 37, p. 6573 - 6576
  • 2
  • [ 591-50-4 ]
  • [ 1453-58-3 ]
  • [ 1128-54-7 ]
YieldReaction ConditionsOperation in experiment
63% With copper(l) iodide; manganese(II) fluoride; (1R,2R)-1,2-diaminocyclohexane; potassium hydroxide In water at 60℃; for 24 h; General procedure: The N-nucleophile (1.47 mmol), CuI (Sigma-Aldrich, 99.999percent purity, 0.147 mmol), MnF2 (Sigma-Aldrich, 98percent purity, 0.441 mmol), KOH (2.94 mmol), the aryl halide (2.21 mmol), trans-1,2-diaminocyclohexane (0.294 mmol) and water (0.75 mL) were added to a reaction vial and a screw cap was fitted to it. The reaction mixture was stirred under air in a closed system at 60C for 24 h. After cooling to room temperature, the mixture was diluted with dichloromethane and filtered through a pad of Celite. The combined organic extracts were dried with anhydrous Na2SO4 and the solvent was removed under reduced pressure. The crude product was purified by silica-gel column chromatography to afford the N-arylated product. The identity and purity of known products was confirmed by 1H and 13C NMR spectroscopic analysis.
Reference: [1] Chemical Communications, 2009, # 41, p. 6258 - 6260
[2] Advanced Synthesis and Catalysis, 2009, vol. 351, # 5, p. 720 - 724
[3] Tetrahedron Letters, 2011, vol. 52, # 52, p. 7171 - 7174
[4] Advanced Synthesis and Catalysis, 2010, vol. 352, # 17, p. 2892 - 2898
  • 3
  • [ 591-50-4 ]
  • [ 1453-58-3 ]
  • [ 1128-54-7 ]
  • [ 6831-91-0 ]
Reference: [1] European Journal of Organic Chemistry, 2004, # 4, p. 695 - 709
[2] Journal of Organic Chemistry, 2007, vol. 72, # 22, p. 8535 - 8538
  • 4
  • [ 591-50-4 ]
  • [ 1221902-70-0 ]
  • [ 14779-17-0 ]
  • [ 1201683-11-5 ]
Reference: [1] New Journal of Chemistry, 2017, vol. 41, # 17, p. 8711 - 8713
  • 5
  • [ 591-50-4 ]
  • [ 1820-80-0 ]
  • [ 1128-56-9 ]
YieldReaction ConditionsOperation in experiment
80% With caesium carbonate; copper(ll) bromide In N,N-dimethyl-formamide at 190℃; for 0.333333 h; Microwave irradiation; Sealed tube 1 -phenyl- 1 H -pyrazol-3-amine 3-Amino-pyrazole (1 .0 g, 12.03 mmol), Cs2CO3 (3.92 g, 12.03 mmol), iodobenzene (3.68 g, 18.05 mmol), CuBr2 (0.268 g, 0.1 mmol), and DMF (4 ml_) were added to a 10-mL microwave vial. The vial was sealed and heated to 190 °C for 20 min (monitored by TLC). After cooling, the reaction mixture was diluted with saturated aqueous ammonium chloride and extracted with ethyl acetate (50 imL x 3). The organic layers were dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo. The crude product was purified by flash column chromatography, eluting with 0-40percent ethyl acetate and petroleum benzine, afforded the desired product, 1 -phenyl-1 -/-pyrazol-3-amine, as a brown solid (1 .53 g, 80percent).
Reference: [1] Bulletin of the Korean Chemical Society, 2012, vol. 33, # 6, p. 2067 - 2070
[2] Patent: WO2015/172196, 2015, A1, . Location in patent: Paragraph 00225
  • 6
  • [ 591-50-4 ]
  • [ 1820-80-0 ]
  • [ 826-85-7 ]
  • [ 1128-56-9 ]
Reference: [1] ChemCatChem, 2015, vol. 7, # 16, p. 2433 - 2436
  • 7
  • [ 591-50-4 ]
  • [ 13826-35-2 ]
Reference: [1] Monatshefte fuer Chemie, 1936, vol. 67, p. 24,35
  • 8
  • [ 591-50-4 ]
  • [ 101-23-5 ]
Reference: [1] New Journal of Chemistry, 2017, vol. 41, # 17, p. 9414 - 9423
  • 9
  • [ 1592-95-6 ]
  • [ 591-50-4 ]
  • [ 1153-85-1 ]
YieldReaction ConditionsOperation in experiment
87.22% With tris-(dibenzylideneacetone)dipalladium(0); tributylphosphine In toluene for 12 h; Heating To a flask including 3-bromo-9H-carbazole and iodobenzene, 0.03 eq. of tris(dibenzilideneacetone)dipalladium(0) (Pd2(dba)3), 0.06 eq. of tributylphosphine, and toluene (0.1 M) were added and stirred for about 12 hours. After that, the reaction product was cooled to ambient temperature, extracted with methylene chloride, and washed with distilled water. The product thus obtained was dried with magnesium sulfate (MgSO4) and distilled under a reduced pressure, and the residue was separated by column chromatography to produce a 3-bromo-9-phenyl-9H-carbazole intermediate (Yield 87.22percent). The mass of the compound identified using a high resolution mass spectrometer (HRMS) was 321, and the molecular formula was identified as C18H12BrN.
86% With tris-(dibenzylideneacetone)dipalladium(0); triphenylphosphine; sodium t-butanolate In toluene at 100℃; To a round bottom flask 3-bromo-9H-carbazole (4.9g, 20mmol), iodobenzene (4.1g, 20mmol), Pd2 (dba) 3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu ( 5.8g, 60mmol), and the reaction allowed to proceed at 100 after the into toluene (210mL). After completion of reaction, the organic layer was dried over MgSO4, and extracted with water and ether and recrystallized silicagel column and the resulting organics concentrated and the product was 5.5g: (yield: 86percent).
86% With copper(l) iodide; 1,10-Phenanthroline; potassium carbonate In 5,5-dimethyl-1,3-cyclohexadiene for 6 h; Reflux 2-neck flask (Two neck flask) the material 1-a '(Cas No. 1592-95-6, 20g, 81.3mmol, 1eq) and iodo benzene (Iodobenzene) (18.23g, 89.4mmol, 1.1eq) was added to . Here, copper iodide (CuI) (3.1g, 16.3mmol, 0.2eq), 1,10- phenanthroline (1,10-phenanthroline) (3.0g, 16.3mmol, 0.2eq), and xylene (xylene) to 150ml then added and stirred under reflux for 6 hours. After the reaction cooled to room temperature, then the solvent was distilled off under reduced pressure and purified by column chromatography to give a 1-b '(22.4g, yield 86percent).
81% With copper; potassium carbonate In nitrobenzene for 16 h; Inert atmosphere; Reflux Under nitrogen atmosphere, intermediate G 2.46g (10mmol) and iodobenzene 3.06g (15mmol) were dissolved in 25ml nitrobenzene, K2CO3 4.15g (30mmol) and Cu 0.19g (3mmol) was added and refluxed for 16 hours. After completion of the reaction, MC 200ml, H2O 200ml was added and then the the MC layer was extracted, concentrated and separated by column chromatography using Hex : EA =5 : 1 and dried over anhydrous MgSO4 to give the intermediate H 2.61g (81percent).
81% With copper; potassium carbonate In nitrobenzene for 16 h; Inert atmosphere; Reflux Under nitrogen intermediates C 2.46g (10mmol) and iodo-benzene 3.06g (15mmol) dissolved in 25ml of nitrobenzene and then, 4.15g K2CO3 (30mmol) and 0.19g Cu (3mmol) were added andIt was refluxed for 16 hours When the reaction is complete, remove the nitrobenzene via distillation, and 200ml MC, was added 200ml of H2O, extract the MC layer was dried over anhydrous MgSO4 and concentrated to Hex: MC = 5: 1 column with an intermediate D 2.61g (81percent to ) to give
79% With copper; potassium carbonate; sodium sulfate In nitrobenzene at 200℃; intermediate G and 1mol iodobenzene nitrobenzene in the 1.5mol It was dissolved, Na2SO4, K2CO3, and the addition of Cu, which was stirred at 200 °. After the reaction is complete when the nitrobenzene removed by distillation and extracted with water and CH2Cl2 and the organic layer over anhydrous MgSO4 In dry, concentrated, and then the desired product was produced by column chromatography and recrystallization To give the intermediate H (Yield: 79percent).
78% With tris-(dibenzylideneacetone)dipalladium(0); triphenylphosphine; sodium t-butanolate In toluene at 100℃; for 24 h; To a round bottom flask Sub 2-1-1 (4.9g, 20mmol), Sub 2-1-2-1 (4.1g, 20mmol),Pd2 (dba) 3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol ), NaOt-Bu (5.8g, 60mmol), were addedto toluene (210mL), respectively, and refluxed under stirring for 24 hours at 100 ° C.ether and with water, dried over MgSO4 and the organic layer was extracted andconcentrated and to the resulting organic silicagel column and recrystallized Sub the 2-1-3-1 5.0g (yield: 78percent) was obtained.
75% With tris-(dibenzylideneacetone)dipalladium(0); triphenylphosphine; sodium t-butanolate In toluene at 100℃; To a round bottom flask Sub 1-1-1 (4.9g, 20mmol), Sub 1-2-1 (4.1g, 20mmol), Pd2 (dba) 3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol), and the reaction proceeds at 100°C after the into toluene (210mL). After the reaction was completed with water and extracted with ether. The organic layer was dried over MgSO4, concentrated and the resulting organic matter by silicagel column and recrystallized 4.8g of Sub 1 (1) (yield: 75percent) was obtained.
75% With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate In toluene at 100℃; In round bottom flask SM-1 (4.9g, 20mmol), SM-2-1 (4.48g, 22mmol), Pd2(dba)3(0.3g, 0.6mmol), P(t-Bu)3(0.2g, 2mmol), t-BuONa (5.8g, 60mmol), toluene (300 ml) added, the reaction proceeds at 100 °C after loading. After completion of reaction was obtained with CH2Cl2 and the organic layer was extracted with water, dried over MgSO4, silicagel column and re-crystallization and the resulting organics concentrated to the 4.8g SM-3-1. (Yield: 75percent)
73% With copper; potassium carbonate; sodium sulfate In nitrobenzene at 200℃; The Sub 1-II-1 (35.25 g, 143.2 mmol) toa round bottom flask in nitrobenzene (1790ml) to dissolve and then, iodobenzene(43.83 g, 214.9 mmol), Na2SO4 (20.35 g, 143.2 mmol), K2CO3 (19.80 g, 143.2mmol), was added Cu (2.73g, 43.0 mmol) and stirred at 200 . After completion ofreaction was removed by distillation to nitrobenzene and extracted with waterand CH2Cl2. The resulting compound and the organic layer was dried over MgSO4and concentrated to silicagel column and the product was recrystallized from 33.69 g (yield: 73percent) was obtained.
72% With copper; potassium carbonate; sodium sulfate In nitrobenzene at 200℃; Said Sub 1-II-1 obtained in the synthesis (110.36g, 448.4mmol) senses a rotation velocity of the disk in nitrobenzene for in round bottom flask , iodobenzene (137.23g, 672.7mmol), Na2SO 4 (63.7g, 448.4mmol), K2CO3 (61.98g, 448.4mmol), cu (8.55g, 134.5mmol) added 200 °C stirring section. When reaction is completed the via fractional distillation to remove the nitrobenzene CH 2 Cl 2 extracted and water. Organic layer MgSO 4 to dry a silicagel column with a compound formed after the products and recrystallization 104.03g (yield 72percent)is obtained
57% With 18-crown-6 ether; copper; sodium t-butanolate In toluene at 100℃; for 24 h; bromo-9H-carbazole (50.0 g, 203 mmol) and iodobenzene (49g, 240 mmol), 800 mL of toluene to the mixture after the Cu (764mg, 12 mmol) ,18-Crown-6 (6.3 g, 24 mmol), NaOt- Bu (57.6 g, 600mmol) each added one after, 100°C in 24 hours stirring under reflux causes. ether and water and the organic layer was extracted and then dried with MgSO4 and then concentrated to produce an organic silicagel column and recrystallized Sub 1-1(1) to give 36.6g). (Yield: 57percent)
1.9 g
Stage #1: With tri-tert-butyl phosphine; palladium diacetate In toluene at 20℃; for 1 h; Inert atmosphere
Stage #2: With potassium carbonate In toluene at 80℃; for 6 h; Inert atmosphere
250ml 3 neck round bottom flask the compound 1-3 (5g), Palladium (II) diacetate (0.1g), Tri-tert-butylphosphine (0.3g), toluene(100ml) was stirred into the atmosphere of argon at room temperature for 1 hour. A mixture of potassium carbonate (7.2g), 3-bromo carbazole (6.3g) it was stirred for 6 hours at 80°C. After the addition of water extracted with ethyl acetate and the title through a separation column using hexane and the resulting material water was removed to give a substituent 1-4 1.9g

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[16] Patent: KR101507423, 2015, B1, . Location in patent: Paragraph 0167-0173
[17] Patent: KR2015/136712, 2015, A, . Location in patent: Paragraph 0086; 0087; 0088; 0089
[18] Journal of Materials Chemistry C, 2017, vol. 5, # 6, p. 1452 - 1462
  • 10
  • [ 4630-20-0 ]
  • [ 591-50-4 ]
  • [ 1153-85-1 ]
YieldReaction ConditionsOperation in experiment
78.8% With copper; potassium carbonate In (2)H8-toluene at 150℃; for 24 h; Inert atmosphere 1) in a 250ml three-neck bottle, under the protection of nitrogen, add 0.05mol 3-bromo-9H-carbazole, 0.06mol iodobenzene, 150ml toluene, stir and mix, then add 0.015mol Cu, 0.15mol potassium carbonate, heated to 150 °C , reflux reaction for 24 hours,Sampling point plate, showing no remaining 3-bromo-9H-carbazole, complete reaction; naturally cooled to room temperature, filtered,The filtrate was evaporated under reduced pressure (-0.09 MPa, 85°C) and passed through a neutral silica gel column to give 3-bromo-9-phenyl-9H-carbazole, HPLC purity 99.3percent, yield 78.8percent;
Reference: [1] Patent: CN108003089, 2018, A, . Location in patent: Paragraph 0081; 0082; 0090
  • 11
  • [ 591-50-4 ]
  • [ 1153-85-1 ]
Reference: [1] Patent: EP2343277, 2011, A2,
[2] Bulletin of the Korean Chemical Society, 2011, vol. 32, # 3, p. 841 - 846
[3] Journal of Materials Chemistry, 2011, vol. 21, # 25, p. 9139 - 9148
[4] Patent: EP2857395, 2015, A1,
[5] Dyes and Pigments, 2015, vol. 117, p. 141 - 148
[6] Patent: CN104370904, 2016, B,
[7] Journal of Organometallic Chemistry, 2017, vol. 829, p. 92 - 100
[8] Patent: KR2017/58874, 2017, A,
[9] Dyes and Pigments, 2018, vol. 156, p. 369 - 378
  • 12
  • [ 591-50-4 ]
  • [ 6630-33-7 ]
  • [ 13047-06-8 ]
Reference: [1] Organic and Biomolecular Chemistry, 2018, vol. 16, # 2, p. 208 - 212
  • 13
  • [ 591-50-4 ]
  • [ 201230-82-2 ]
  • [ 244205-40-1 ]
  • [ 13047-06-8 ]
Reference: [1] ChemSusChem, 2018, vol. 11, # 19, p. 3382 - 3387
  • 14
  • [ 591-50-4 ]
  • [ 79-41-4 ]
  • [ 1199-77-5 ]
YieldReaction ConditionsOperation in experiment
62% at 80℃; Micellar solution A typical Heck reaction was performed in a double walledglass reactor with reflux condenser at ambient pressure. 153 μL (1.34 mmol) alkene (e.g. styrene) and 158 L (1.50 mmol) arylhalide (e.g. iodobenzene) were dissolved in 46 mL organic sol-vent or aqueous microemulsion in the presence of 0.276 g(2.00 mmol) K2CO3as base and stirred at desired reactiontemperature.1.2–1.4 g of the immobilized catalyst containing15 mg (0.067 mmol) Pd(OAc)2on silica was added to the reactionmixture and the reaction was started. For the Heck reaction withhomogeneous catalyst only 15 mg (0.067 mmol) of palladium (II)acetate was added. The reaction progress was monitored by mea-suring the reactant concentrations at different reaction times byhigh performance liquid chromatography (HPLC).
Reference: [1] Journal of Molecular Catalysis A: Chemical, 2014, vol. 393, p. 210 - 221
  • 15
  • [ 591-50-4 ]
  • [ 10401-11-3 ]
Reference: [1] Journal of the Chemical Society, Chemical Communications, 1991, # 22, p. 1630 - 1632
  • 16
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  • [ 79991-24-5 ]
  • [ 105946-82-5 ]
  • [ 130201-21-7 ]
Reference: [1] Canadian Journal of Chemistry, 1982, vol. 60, p. 990 - 999
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Reference: [1] Advanced Synthesis and Catalysis, 2008, vol. 350, # 3, p. 395 - 398
[2] Journal of Organometallic Chemistry, 2010, vol. 695, # 14, p. 1768 - 1775
[3] Organometallics, 2012, vol. 31, # 21, p. 7336 - 7338
[4] Monatshefte fur Chemie, 2011, vol. 142, # 8, p. 801 - 806
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  • [ 95-53-4 ]
  • [ 1205-39-6 ]
  • [ 4316-55-6 ]
Reference: [1] Tetrahedron Letters, 2002, vol. 43, # 40, p. 7143 - 7146
  • 19
  • [ 591-50-4 ]
  • [ 1483-72-3 ]
Reference: [1] Organic and Biomolecular Chemistry, 2011, vol. 9, # 14, p. 5039 - 5042
  • 20
  • [ 591-50-4 ]
  • [ 71-43-2 ]
  • [ 1483-72-3 ]
Reference: [1] Letters in Organic Chemistry, 2013, vol. 10, # 8, p. 541 - 548
  • 21
  • [ 591-50-4 ]
  • [ 103962-05-6 ]
  • [ 175278-00-9 ]
  • [ 198206-33-6 ]
Reference: [1] Angewandte Chemie - International Edition, 2018, vol. 57, # 42, p. 13784 - 13789[2] Angew. Chem., 2018, vol. 130, p. 13980 - 13985,6
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  • [ 625-92-3 ]
  • [ 591-50-4 ]
  • [ 142137-17-5 ]
Reference: [1] Synlett, 2002, # 6, p. 1008 - 1010
  • 23
  • [ 13535-01-8 ]
  • [ 591-50-4 ]
  • [ 73183-34-3 ]
  • [ 142137-17-5 ]
Reference: [1] Journal of Organic Chemistry, 2013, vol. 78, # 5, p. 1923 - 1933
  • 24
  • [ 591-50-4 ]
  • [ 73819-76-8 ]
  • [ 119389-05-8 ]
Reference: [1] New Journal of Chemistry, 2015, vol. 39, # 4, p. 2925 - 2934
  • 25
  • [ 591-50-4 ]
  • [ 60511-85-5 ]
  • [ 1024598-06-8 ]
YieldReaction ConditionsOperation in experiment
65% With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate In toluene for 3 h; Inert atmosphere; Reflux According to the preparation method of compound 66 in Example 3,the difference is,The synthetic route used is the above route,Using compound 113 'instead of carbazole,Using iodobenzene instead of compounds 1-5,To give compound 113-1 (yield 65percent)
Compound 1-5 (0.1623 mol) was added to toluene (450 mL)And then carbazole (0.1623 mol) was added under nitrogen protection,Sodium tert-butoxide (0.3246 mol), Pd2 (dba) 3 (0.0016 mol)And tri-tert-butylphosphine (0.0016 mol)And heated to reflux for 3 h,The silica gel funnel was filtered and the resulting filtrate was evaporated to dryness. The resulting solid was recrystallized from toluene to give compound 66 (yield 48percent):
64% With 18-crown-6 ether; copper; potassium carbonate In 1,2-dichloro-benzene for 12 h; Reflux; Inert atmosphere to a 2-neck round bottom flask under nitrogen a mixture of B-1 2.1g (0.0082mol), iodo- benzene (Iodobenzene) 2.5g(0.013mol), Cu 0.312g (0.0049), 18- crown-6-ether (18-crown- 6-ether) 0.433g (0.0016mol), K2CO3 3.397g (0.0246mol) and o-DCB 20ml was stirred under reflux for 12 hours.The solution cooled to room temperature was extracted and concentrated by MC / H2O and separated with column chromatography (SiO2, Hexane:ethyl acetate = 10: 1) to obtain the title compound 2-B (1.76g, 64percent) as a white solid.
64% With 18-crown-6 ether; copper In 1,2-dichloro-benzene for 12 h; Reflux; Inert atmosphere Under nitrogen Two neck round bottom flask (rbf two neck: two neck round bottom flask) to the C-1 (2.1g, 0.0082mol), iodo- benzene (Iodobenzene) (2.5g, 0.013mol), Cu (0.312g , .0049), 18-crown-6-ether (18-Crown-6-ether) (0.433g, 0.0016mol), potassium carbonate (3.397g, 0.0246mol), ortho-dichlorobenzene in the mixture (20ml), It was stirred under reflux for 12 hour. Concentrated by extracting the solution cooled to room temperature with methylene chloride / H2O and purified by column chromatography (SiO2, hexane: ethyl acetate = 10: 1) to obtain a white solid compound C-2 by (1.76g, 64percent).
64% With 18-crown-6 ether; copper; potassium carbonate In 1,2-dichloro-benzeneInert atmosphere; Reflux Under nitrogen tunek round bottom flask (two neck round bottom flask) to A-1 (2.1g, 0.0082mol), Iodobenzene 2.5g (0.013mol), Cu 0.312g (0.0049 mol), 18-crown-6-ether 0.433g (0.0016mol), 20 ml of o-dichlorobenzene,K2CO3 (3.397g, 0.0246mol) was stirred under reflux for 16 hours . The solution was cooled to room temperature, MC (methylene chloride) / H2O and extracted with concentrated and separated by column chromatography (SiO2, hexane,ethyl acetate) 1/10) to give a white solid compound A-2 (1.76g , 64percent).
64% With 18-crown-6 ether; copper; potassium carbonate In 1,2-dichloro-benzeneReflux The compounds in the original neck rbf a nitrogen filled 250-2 (2.1g, 1.0eq), iodo-benzene (2.5g, 1.5eq), Cu (0.312g, 0.6eq), 18- crown-6-ether (0.433g , 0.2eq), a mixture of K2CO3 (3.397g, 3.0eq), 1,2- dichlorobenzene (20) was stirred for 16 hours at reflux temperature. The solution was concentrated and cooled to room temperature and extracted with MC / H2O and purified by column chromatography (SiO2, hexane: 1: ethyl acetate = 10) to obtain a white solid compound 250-3 separated by (1.76g, 64percent).
64% With 18-crown-6 ether; copper; potassium carbonate In 1,2-dichloro-benzene for 16 h; Reflux A mixture of compound 73-2 (2.1 g, 1.0 equiv.),Iodobenzene (2.5 g, 1.5 eq.),Cu (0.312 g, 0.6 equiv),18-Crown-6-ether (0.433 g, 0.2 equiv),K2CO3 (3.397 g, 3.0 eq)And 1,2-dichlorobenzene (20 ml) was stirred at reflux temperature for 16 hours.The solution cooled to room temperature was extracted with MC / H2O and concentrated,And then purified by column chromatography (SiO2, hexane: ethyl acetate = 10: 1)Compound 73-3 (1.76 g, 64percent) was isolated as a white solid.
64% With 18-crown-6 ether; copper; potassium carbonate In 1,2-dichloro-benzene for 16 h; Inert atmosphere; Reflux A mixture of Compound B-1 (2.1 g, 0.0082 mol), iodobenzene (2.5 g, 0.013 mol), Cu (0.312 g, 0.0049), 18-crown-6-ether (0.433 g, 0.0016 mol), K2CO3(3.397 g, 0.0246 mol), and o-dichlorobenzene (o-DCB) (20 ml) was refluxed and stirred in a two neck round bottom flask (two neck r.b.f) under nitrogen for 16 hours. The mixed solution cooled to room temperature was extracted with MC (methylene chloride)/H2O and concentrated and separated by column chromatography (SiO2, hexane:ethyl acetate=10:1). As a result, a white solid compound B-2 was obtained (1.76 g, 64percent).
64% With 18-crown-6 ether; copper; potassium carbonate In 1,2-dichloro-benzeneInert atmosphere; Reflux Under nitrogen, compound B-1 (2.1 g, 0.0082 mol), Iodobenzene (2.5 g, 0.013 mol), Cu (0.312 g, 0.0049), 18-crown-6-ether (0.433 g, 0.0016 mol), and K2CO3 (3.397g, 0.0246 mol) in o-dichlorobenzene (o-DCB) (20 ml) was stirred at reflux condition for 16 hours. The solution cooled to room temperature was extracted with dichloromethane/H2O, concentrated and subjected to column chromatography (SiO2, hexane:ethyl acetate=10:1) to obtain white solid compound B-2 was obtained (1.76 g, 64percent).
64% With 18-crown-6 ether; copper; potassium carbonate In 1,2-dichloro-benzene for 12 h; Reflux; Inert atmosphere To a 2 neck round bottom flask under nitrogen was added the compound B-1 (2.1 g, 0.0082 mol), iodobenzene (Iodobenzene, 2.5 g,0.013 mol), Cu (0.312 g, 0.0049 mol), 18-crown-6-ether (0.433 g, 0.0016 mol)A mixture of o-DCB (20 ml) of K2CO3 (3.397 g, 0.0246 mol) was refluxed for 12 hours. The solution cooled to room temperature was washed with MC / H2O, And concentrated by column chromatography (SiO2, hexane: Ethyl acetate = 10: 1) to obtain white solidWater B-2 was obtained (1.76 g, 64percent).
64% With tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate In toluene for 3 h; Reflux; Inert atmosphere The intermediate of indolocarbazole, benzene iodide (1.1 equivalent), bisdibenzylidene acetone palladium (0) (0.03 equivalent), tri-t-butylphosphine (1 equivalent), and sodium t-butoxide (2 equivalent) was added to toluene under an nitrogen environment, and the mixture was heated and refluxed for 3 hours. When a reaction was complete, the reaction solution was once filtered at a high temperature, twice extracted with brine, and an organic layer extracted therefrom was dried and concentrated. The concentrated solution was added to methanol in a dropwise fashion to obtain a solid, and a residue obtained after filtering the solid was separated and purified through column chromatography to obtain Intermediate of phenyl-indolocarbazole (64percent).
41% at 190℃; for 72 h; Inert atmosphere Example 1; Synthesis of Compound 1-19; Under a nitrogen atmosphere, 26.0 g (0.10 mol) of IC-1, 122.7 g (0.60 mol) of iodobenzene, 54.7g (0.29 mol) of copper iodide, 66.7 g (0.48 mol) of potassium carbonate, and 800 ml of quinoline were stirred for 72 hours while being heated at 190°C. The reaction solution wascooled toroomtemperature. Afterthat, distilledwater (500 ml) and dichloromethane (500 ml) were then added while being stirred. The precipitated crystal was separated by filtration. The organic layer was then washed with distilled water (3.x.500 ml). The organic layer was dried over anhydrous magnesium sulfate. The magnesium sulfate was then separated by filtration and the solvent was subjected to vacuum distillation. The resultant residue was purified by silica gel column chromatography to afford 13.7 g (41percent yield) of an intermediate B as a white solid.
40.6% at 190℃; for 72 h; In a 1000-ml three-necked flask that had been deaerated and filled with nitrogen were placed 26.0 g (101.4 mmol) of the white powder obtained above, 122.7 g (601.4 mmol) of iodobenzene, 54.7 g (287.2 mmol) of copper iodide, 66.7g (482.6 mmol) of potassium carbonate, and 800 ml of quinoline and stirred. The mixture was then heated to 190°C and stirred at this temperature for 72 hours. The mixture was cooled to room temperature, 500 ml of water and 500 ml of dichloromethane were added, the mixture was stirred, and the yellow crystals formed were filtered. The filtrate was transferred to a 2000-ml separatory funnel and separated into the organic layer and the aqueous layer. The organic layer was washed three times with 500 ml of water, dehydrated over magnesium sulfate, the magnesium sulfate was filtered, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to give 13.7 g (41.2 mmol, 40.6percent yield) of a white powder.; Then, 26.0 g (101.4 mmol) of the white powder obtained above, 122.7 g (601.4 mmol) of iodobenzene, 54.7 g (287.2 mmol) of copper iodide, 66.7 g (482.6 mmol) of potassium carbonate, and 800 ml of quinoline were placed in a 1000-ml three-necked flask that had been deaerated and filled with nitrogen and stirred. The mixture was then heated to 190°C and stirred at this temperature for 72 hours. The mixture was cooled to room temperature, 500 ml of water and 500 ml of dichloromethane were added, the mixture was stirred, and the yellow crystals formed were filtered. The filtrate was transferred to a 2000-ml separatory funnel and separated into the organic layer and the aqueous layer. The organic layer was washed three times with 500 ml of water, dehydrated over magnesium sulfate, the magnesium sulfate was filtered, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to give 13.7 g (41.2 mmol, 40.6percent yield) of a white powder.; Then, 26.0 g (0.101 mole) of the white powder obtained above, 122.7 g (0.601 mole) of iodobenzene, 54.7 g (0.287 mole) of copper iodide, 66.7 g (0.482 mole) of potassium carbonate, and 800 ml of quinoline were placed in a 1000-ml three-necked flask that had been deaerated and filled with nitrogen and stirred. The mixture was then heated to 190°C and stirred at this temperature for 72 hours. The mixture was cooled to room temperature, 500 ml of water and 500 ml of dichloromethane were added, the mixture was stirred, and the yellow crystals formed were filtered. The filtrate was transferred to a 2000-ml separatory funnel and separated into the organic layer and the aqueous layer. The organic layer was washed three times with 500 ml of water, dehydrated over magnesium sulfate, the magnesium sulfate was filtered, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to give 13.7 g (0.04 mole, 40.8percent yield) of a white powder.
40.6% With potassium carbonate In quinoline at 190℃; for 72 h; In a 1000-ml three-necked flask that had been deaerated and filled with nitrogen were placed 26.0 g (101.4 mmoles) of the white powder obtained above, 122.7 g (601.4 mmoles) of iodobenzene, 54.7 g (287.2 mmoles) of copper iodide, and 66.7 g (482.6 mmoles) of potassium carbonate, then 800 ml of quinoline was added, and the mixture was stirred. The mixture was then heated to 190°C and stirred at this temperature for 72 hours. The mixture was cooled to room temperature, 500 ml of water and 500 ml of dichloromethane were added, the mixture was stirred, and the yellow crystals formed were filtered. The filtrate was transferred to a 2000-ml separatory funnel and separated into an organic layer and an aqueous layer. The organic layer was washed three times with 500 ml of water and dried over magnesium sulfate, the magnesium sulfate was filtered off, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to give 13.7 g (41.2 mmoles, 40.6percent yield) of white solid A or 11-phenylindolo[2,3-a]carbazole.
40.8% at 190℃; for 72 h; Inert atmosphere Next, in a 1,000-ml three-necked flask that had been deaerated and filled with nitrogen were placed 26.0 g (0.101 mole) of the white powder A obtained above, 122.7 g (0.601 mole) of iodobenzene, 54.7 g (0.287 mole) of copper iodide, 66.7 g (0.482 mole) of potassium carbonate, and 800 ml of quinoline and stirred. The mixture was then heated to 190°C and stirred at this temperature for 72 hours. The mixture was cooled to room temperature, 500 ml of water and 500 ml of dichloromethane were added, the mixture was stirred, and the yellow crystals formed were collected by filtration. The filtrate was transferred to a 2,000-ml separatory funnel and separated into an organic layer and an aqueous layer. The organic layer was washed three times with 500 ml of water and then dehydrated over magnesium sulfate, the magnesium sulfate was filtered out, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to give 13.7 g (0.04 mole, 40.8percent yield) of a white powder B.
40.6% at 190℃; for 72 h; Inert atmosphere Next, 26.0 g (0.10 mol) of the white powder obtained in the foregoing, 122.7 g (0.60 mol) of iodobenzene, 54.7 g (0.29 mol) of copper iodide, 66.7 g (0.48 mol) of potassium carbonate, and 800 ml of quinoline were loaded into a 1,000-ml three-necked flask purged with nitrogen and stirred. After that, the mixture was heated to 190° C. and stirred for 72 hr. Once the mixture was cooled to room temperature, and then 500 ml of water and 500 ml of dichloromethane were added to the mixture, followed by stirring. After that, the resultant yellow crystal was taken by filtration. The filtrate was transferred to a 2,000-ml separating funnel, and was fractionated into an organic layer and an aqueous layer. The organic layer was washed with 500 ml of water three times, and then the resultant organic layer was dried with magnesium sulfate. Once magnesium sulfate was separated by filtration and then the solvent was distilled off under reduced pressure. After that, the residue was purified by column chromatography to provide 13.7 g (0.041 mol, yield: 40.6percent) of Intermediate A as a white solid.

Reference: [1] Patent: CN106928237, 2017, A, . Location in patent: Paragraph 0152; 0153; 0154; 0155; 0166-0168
[2] Patent: KR2016/8819, 2016, A, . Location in patent: Paragraph 0189; 0191; 0195; 0196
[3] Patent: KR2015/132019, 2015, A, . Location in patent: Paragraph 0227; 0228; 0231; 0232
[4] Patent: KR2016/1702, 2016, A, . Location in patent: Paragraph 0192-0193; 0196-0197
[5] Patent: KR101551895, 2015, B1, . Location in patent: Paragraph 0307; 0312; 0313
[6] Patent: CN105408333, 2016, A, . Location in patent: Paragraph 0252; 0257; 0258
[7] Patent: KR101558495, 2015, B1, . Location in patent: Paragraph 0342; 0343; 0346; 0347
[8] Patent: KR2016/41019, 2016, A, . Location in patent: Paragraph 0167; 0168; 0172; 0173
[9] Patent: KR2017/2208, 2017, A, . Location in patent: Paragraph 0258-0259; 0263-0264
[10] Patent: US2018/47916, 2018, A1, . Location in patent: Paragraph 0137
[11] Patent: EP2415772, 2012, A1, . Location in patent: Page/Page column 35
[12] Patent: EP1956022, 2008, A1, . Location in patent: Page/Page column 33-34; 36
[13] Patent: EP2080762, 2009, A1, . Location in patent: Page/Page column 24
[14] Patent: EP2166011, 2010, A1, . Location in patent: Page/Page column 20
[15] Patent: US9985219, 2018, B2, . Location in patent: Page/Page column 304; 306
  • 26
  • [ 591-50-4 ]
  • [ 222-19-5 ]
  • [ 1024598-06-8 ]
YieldReaction ConditionsOperation in experiment
51% With potassium phosphate; copper(l) iodide; trans-1,2-cyclohexanediamine In 1,4-dioxane for 24 h; Inert atmosphere; Reflux In an argon atmosphere, 90 ml of dehydrated 1,4-dioxane was added to a mixture of 15.0 g (58.5 mmol) of indolo[2,3-a]carbazole (synthesized according to the method of Synlett p.42-48 (2005)), 11.9 g (58.5 mmol) of iodobenzene, 11.2 g (58.5 mmol) of copper iodide, 20.0 g (175.5 mmol) of trans-1,2-cyclohexanediamine, and 37.3 g (175.5 mmol) of tripotassium phosphate, and the resultant mixture was stirred for 24 h while refluxing under heating. The reaction solution was concentrated under reduced pressure. The obtained residue was added with 500 ml of toluene, heated to 120 °C, and then filtered to remove insolubles. The filtrate was concentrated under reduced pressure and the obtained residue was purified by silica gel column chromatography, to obtain 10.0 g of white solid, which was identified as the following intermediate 2-1 by FD-MS analysis (yield: 51percent).
Reference: [1] Patent: EP2738166, 2014, A1, . Location in patent: Paragraph 0167
  • 27
  • [ 591-50-4 ]
  • [ 1984-49-2 ]
  • [ 1060735-14-9 ]
YieldReaction ConditionsOperation in experiment
5.59 g With copper; potassium carbonate In nitrobenzene at 180℃; for 4 h; Inert atmosphere Then under a nitrogen stream, the 14.0g of 9H, 9'H-3,3'- Dicarbazole,Iodine benzene 8.59 g, nitrobenzene 400ml, 5.72 g of copper powder with 12.44 g of potassium carbonate mixturesolution heated to 180 ° C for 4 hours. After coolingto room temperature, the nitrobenzene was removed by distillation under reducedpressure, followed by purification by silica gel chromatography, vacuum dryingto obtain 5.59g of 9-phenyl-9H, 9H-3,3-dicarbazole.
Reference: [1] Patent: TWI523840, 2016, B, . Location in patent: Page/Page column 52
  • 28
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  • [ 1060735-14-9 ]
Reference: [1] Patent: KR2015/133998, 2015, A,
[2] Patent: KR2017/58874, 2017, A,
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  • [ 98-80-6 ]
  • [ 591-50-4 ]
  • [ 1008106-86-2 ]
Reference: [1] Catalysis Communications, 2013, vol. 32, p. 15 - 17
  • 30
  • [ 591-50-4 ]
  • [ 864172-93-0 ]
  • [ 1316216-05-3 ]
YieldReaction ConditionsOperation in experiment
38% With caesium carbonate In tetraethoxy orthosilicate at 140℃; for 14 h; A mixture of the compound 2 (6.2 g, 25 mmol), iodobenzene (6.12 g, 30 mmol), Cul (955 mg, 5.0 mmol), CS2CO3 (16.3 g, 50 mmol) in TEOS (200 ml) was degassed and purged with nitrogen. The resulting mixture was stirred at 140 °C for 14h. After cooling to rt, the residue was diluted with EtOAc (200 ml) and 95percentEtOH (200 ml), NH4F-H20 on silica gel [50g, pre- prepared by the addition of NH4F (lOOg) in water (1500 ml) to silica gel (500g, 100- 200mesh)] was added, and the resulting mixture was kept at rt for 2 h, the solidified materials was filtered and washed with EtOAc. The filtrate was evaporated to dryness and the residue was purified by silica gel chromatography (petroleum ethers/EtOAc = 10/1) to give a yellow solid (3 g, 38 percent).
38% at 140℃; for 14 h; Inert atmosphere Synthesis of Intermediate 3A mixture of the compound 2 (6.2 g, 25 mmol), iodobenzene (6.12 g, 30 mmol), Cul (955 mg, 5.0 mmol), Cs2C03 (16.3 g, 50 mmol) in tetraethyl orthosilicate (TEOS) (200 ml) was degassed and purged with nitrogen. The resulting mixture was stirred at 140 °C for 14h. After cooling to rt, the residue was diluted with EtOAc (200 ml) and95percentEtOH (200 ml), NH4F-H20 on silica gel [50g, pre-prepared by the addition of NH4F (lOOg) in water (1500 ml) to silica gel (500g, 100-200mesh)] was added, and the resulting mixture was kept at room temperature for 2 h, the solidified materials was filtered and washed with EtOAc. The filtrate was evaporated to dryness and the residue was purified by silica gel chromatography (petroleum ethers/EtOAc = 10/1) to give a yellow solid (3 g, 38 percent).
38% at 140℃; for 14 h; Inert atmosphere [0234] A mixture of compound 2 (6.2 g, 25 mmol), iodobenzene (6.12 g, 30 mmol), CuI (955 mg, 5.0 mmol), Cs2CO3 (16.3 g, 50 mmol) in TEOS (200 ml) was degassed and purged with nitrogen. The resulting mixture was stirred at 140° C. for 14 hrs. After cooling to r.t., the residue was diluted with EtOAc (200 ml). 95percent EtOH (200 ml) and NH4F—H2O on silica gel [50 g, pre-prepared by the addition of NH4F (100 g) in water (1500 ml) to silica gel (500 g, 100-200 mesh)] was added, and the resulting mixture was kept at r.t. for 2 hrs. The solidified materials were filtered and washed with EtOAc. The filtrate was evaporated to dryness and the residue was purified by silica gel chromatography (petroleum ethers/EtOAc=10/1) to give a yellow solid (3 g, 38percent).
38% at 140℃; for 14 h; Inert atmosphere A mixture of compound 2 (6.2 g, 25 mmol), iodobenzene (6.12 g, 3Ommol), Cul (955 mg, 5.Ommol), Cs2CO3 (16.3 g, 50 mmol) in TEOS (200 ml) was degassed and purged with nitrogen. The resulting mixture was stirred at 140°C. for 14 hrs. Afier cooling to tt., the residue was diluted with EtOAc (200 ml). 95percent EtOR (200 ml) and NH4F—H20 on silica gel [50 g, pre-prepared by the addition of NH4F (100 g) in water (1500 ml) to silica gel (500 g, 100-200 mesh)] was added, and the resulting mixture was kept at tt. for 2 hrs. The solidified materials were filtered and washed with EtOAc. The filtrate was evaporated to dryness and the residue was purified by silica gel chromatography (petroleum ethers EtOAc=10/1) to give a yellow solid (3 g, 38percent).
38% at 140℃; for 14 h; Inert atmosphere Synthesis of Intermediate 3 A mixture of the compound 2 (6.2 g, 25 mmol), iodobenzene (6.12 g, 30 mmol), CuI (955 mg, 5.0 mmol), Cs2CO3 (16.3 g, 50 mmol) in TEOS (200 ml) was degassed and purged with nitrogen. The resulting mixture was stirred at 140° C. for 14 h. After cooling to rt, the residue was diluted with EtOAc (200 ml) and 95percent EtOH (200 ml), NH4F—H2O on silica gel [50 g, pre-prepared by the addition of NH4F (100 g) in water (1500 ml) to silica gel (500 g, 100-200 mesh)] was added, and the resulting mixture was kept at rt for 2 h, the solidified materials was filtered and washed with EtOAc. The filtrate was evaporated to dryness and the residue was purified by silica gel chromatography (petroleum ethers/EtOAc=10/1) to give a yellow solid (3 g, 38percent).
38% at 140℃; for 14 h; Inert atmosphere Synthesis of Intermediate 3 [0155] A mixture of the compound 2 (6.2 g, 25 mmol), iodobenzene (6.12 g, 30 mmol), CuI (955 mg, 5.0 mmol), Cs2CO3 (16.3 g, 50 mmol) in TEOS (200 ml) was degassed and purged with nitrogen. The resulting mixture was stirred at 140° C. for 14 h. After cooling to r.t., the residue was diluted with EtOAc (200 ml) and 95percent EtOH (200 ml), NH4F—H2O on silica gel [50 g, pre-prepared by the addition of NH4F (100 g) in water (1500 ml) to silica gel (500 g, 100-200 mesh)] was added, and the resulting mixture was kept at r.t. for 2 h, the solidified materials was filtered and washed with EtOAc. The filtrate was evaporated to dryness and the residue was purified by silica gel chromatography (petroleum ethers/EtOAc=10/1) to give a yellow solid (3 g, 38percent).
38% at 140℃; for 14 h; Inert atmosphere A mixture of compound 2 (6.2 g, 25 mmol), iodobenzene (6.12 g, 30 mmol), CuI (955 mg, 5.0 mmol), Cs2CO3 (16.3 g, 50 mmol) in TEOS (200 ml) was degassed and purged with nitrogen. The resulting mixture was stirred at 140° C. for 14 hrs. After cooling to r.t., the residue was diluted with EtOAc (200 ml). 95percent EtOH (200 ml) and NH4F—H2O on silica gel [50 g, pre-prepared by the addition of NH4F (100 g) in water (1500 ml) to silica gel (500 g, 100-200 mesh)] was added, and the resulting mixture was kept at r.t. for 2 hrs. The solidified materials were filtered and washed with EtOAc. The filtrate was evaporated to dryness and the residue was purified by silica gel chromatography (petroleum ethers/EtOAc=10/1) to give a yellow solid (3 g, 38percent).
38% at 140℃; for 14 h; Inert atmosphere A mixture of compound 2 (6.2 g, 25 mmol), iodobenzene (6.12 g, 30 mmol), CuI (955 mg, 5.0 mmol), Cs2CO3 (16.3 g, 50 mmol) in TEOS (200 ml) was degassed and purged with nitrogen. The resulting mixture was stirred at 140° C. for 14 hrs. After cooling to r.t., the residue was diluted with EtOAc (200 ml). 95percent EtOH (200 ml) and NH4F—H2O on silica gel [50 g, pre-prepared by the addition of NH4F (100 g) in water (1500 ml) to silica gel (500 g, 100-200 mesh)] was added, and the resulting mixture was kept at r.t. for 2 hrs. The solidified materials were filtered and washed with EtOAc. The filtrate was evaporated to dryness and the residue was purified by silica gel chromatography (petroleum ethers/EtOAc=10/1) to give a yellow solid (3 g, 38percent).
38% at 140℃; for 14 h; Inert atmosphere Synthesis of Intermediate 3 [0248] [0249] A mixture of the compound 2 (6.2 g, 25 mmol), iodobenzene (6.12 g, 30 mmol), CuI (955 mg, 5.0 mmol), Cs2CO3 (16.3 g, 50 mmol) in TEOS (200 ml) was degassed and purged with nitrogen. The resulting mixture was stirred at 140° C. for 14 h. After cooling to rt, the residue was diluted with EtOAc (200 ml) and 95percent EtOH (200 ml), NH4F—H2O on silica gel [50 g, pre-prepared by the addition of NH4F (100 g) in water (1500 ml) to silica gel (500 g, 100-200 mesh)] was added, and the resulting mixture was kept at rt for 2 h, the solidified materials was filtered and washed with EtOAc. The filtrate was evaporated to dryness and the residue was purified by silica gel chromatography (petroleum ethers/EtOAc=10/1) to give a yellow solid (3 g, 38percent).
38% at 140℃; for 14 h; Inert atmosphere Synthesis of Intermediate 3: A mixture of compound 2 (6.2 g, 25 mmol), iodobenzene(6.12 g, 3Ommol), Cul (955 mg, 5.Omrnol), Cs2CO3(16.3 g, SOmmol) inTEOS (200m1)was degassed and purged with nitrogen. The resulting mixture was stirred at 140°C for 14hrs. After cooling to r.t., the residue was diluted with EtOAc (200 ml). 95percent EtOH (200 ml)and NH4F-H20 on silica gel [50g, pre-prepared by the addition ofNH4F (bOg) in water(1500 ml) to silica gel (500g, 100-200 mesh)] was added, and the resulting mixture was kept at r.t. for 2 hrs. The solidified materials were filtered and washed with EtOAc. The filtrate was evaporated to dryness and the residue was purified by silica gel chromatography(petroleum ethers/EtOAc = 10/1) to give a yellow solid (3 g, 38percent).
38% at 140℃; for 14 h; Inert atmosphere A mixture of the compound 2 (6.2 g, 25 mmol),iodobenzene (6.12 g, 30 mmol), Cul (955 mg, 5.0 mmol), Cs2CO3 (16.3 g, 50 mmol) inTEOS (200 ml) was degassed and purged with nitrogen. The resulting mixture was stirred at140 °C for 14h. After cooling to rt, the residue was diluted with EtOAc (200 ml) and95percentEtOH (200 ml), NH4F-H20 on silica gel [50g, pre-prepared by the addition of NH4F(bOg) in water (1500 ml) to silica gel (500g, 100-200mesh)] was added, and the resultingmixture was kept at rt for 2 h, the solidified materials was filtered and washed with EtOAc.The filtrate was evaporated to dryness and the residue was purified by silica gel chromatography (petroleum ethers/EtOAc = 10/1) to give a yellow solid (3 g, 38 percent).
38% at 140℃; for 14 h; Inert atmosphere A mixture of compound 2 (6.2 g, 25 mmol), iodobenzene (6.12 g, 30 mmol), Cul (955 mg, 5.0 mmol), Cs2CO3 (16.3 g, 50 mmol) in TEOS (200 ml) was degassed and purged with nitrogen. The resulting mixture was stirred at 140° C. for 14 hrs. Afier cooling to tt., the residue was diluted with EtOAc (200 ml). 95percent EtOR (200 ml) and NH4F—H20 on silica gel [50 g, pre-prepared by the addition of NH4F (100 g) in water (1500 ml) to silica gel (500 g, 100-200 mesh)] was added, and the resulting mixture was kept at tt. for 2 hrs. The solidified materials were filtered and washed with EtOAc. The filtrate was evaporated to dryness and the residue was purified by silica gel chromatography (petroleum ethers/EtOAc=10/1) to give a yellow solid (3 g, 38percent).
38% at 140℃; for 14 h; Inert atmosphere A mixture of compound 2 (6.2 g, 25 mmol), iodobenzene (6.12g, 30 mmol), CuT (955 mg, 5.0 mmol), Cs2CO3 (16.3 g, 50 mmol) in TEOS (200 ml) was degassed and purged with nitrogen. The resulting mixture was stirred at 140 °C for 14 hrs. After cooling to r.t., the residue was diluted with EtOAc (200 ml). 95percent EtOH (200 ml) andNH4F-H20 on silica gel [50g, pre-prepared by the addition of NH4F (bOg) in water (1500 ml) to silica gel (500g, 100-200 mesh)] was added, and the resulting mixture was kept at r.t. for 2 hrs. The solidified materials were filtered and washed with EtOAc. The filtrate wasevaporated to dryness and the residue was purified by silica gel chromatography (petroleum ethers/EtOAc = 10/1) to give a yellow solid (3 g, 3 8percent).
38% at 140℃; for 14 h; Inert atmosphere A mixture of the compound 2 (6.2 g, 25 mmol), iodobenzene (6.12 g, 30 mmol), CuI (955 mg, 5.0 mmol), Cs2CO3 (16.3 g, 50 mmol) in TEOS (200 ml) was degassed and purged with nitrogen. The resulting mixture was stirred at 140° C. for 14 h. After cooling to rt, the residue was diluted with EtOAc (200 ml) and 95percent EtOH (200 ml), NH4F—H2O on silica gel [50 g, pre-prepared by the addition of NH4F (100 g) in water (1500 ml) to silica gel (500 g, 100-200 mesh)] was added, and the resulting mixture was kept at rt for 2 h, the solidified materials was filtered and washed with EtOAc. The filtrate was evaporated to dryness and the residue was purified by silica gel chromatography (petroleum ethers/EtOAc=10/1) to give a yellow solid (3 g, 38percent).
38% at 140℃; for 14 h; Inert atmosphere 0127] A mixture of intermediate 2 (6.2 g, 25 mmol), iodobenzene (6.12 g, 30 mmol), Cul (955 mg, 5.0 mmol), Cs2CO3 (16.3 g, 50 mmol) in TEOS (200 mL) was degassed and purged with nitrogen. The resulting mixture was stirred at 140°C for 14 h. After cooling to rt, the residue was diluted with EtOAc (200 mL) and 95percent EtOH (200 mL), NH4F-H2O on silica gel [50 g, pre-prepared by the addition of NH4F (100 g) in water (1500 mL) to silica gel (500 g, 100-200 mesh)] was added and the resulting mixture was kept at rt for 2h, the solidified materials was filtered and washed with EtOAc. The filtrate was evaporated to dryness and the residue was purified by silica gel chromatography (petroleum ethers/EtOAc=10/1) to give a yellow solid (3 g, 38percent).
38% at 140℃; for 14 h; Inert atmosphere A mixture of the compound 2 (6.2 g, 25 mmol), iodobenzene (6.12 g, 30 mmol), Cul (955 mg, 5.0 mmol), Cs2C03 (16.3 g, 50 mmol) in TEOS (200 ml) was degassed and purged with nitrogen. The resulting mixture was stirred at 140 °C for 14h. After cooling to rt, the residue was diluted with EtOAc (200 ml) and 95percentEtOH (200 ml), H4F-H20 on silica gel [50g, pre-prepared by the addition of H4F (lOOg) in water (1500 ml) to silica gel (500g, 100-200mesh)] was added, and the resulting mixture was kept at rt for 2 h, the solidified materials was filtered and washed with EtOAc. The filtrate was evaporated to dryness and the residue was purified by silica gel chromatography (petroleum ethers/EtOAc = 10/1) to give a yellow solid (3 g, 38 percent).
38% at 140℃; for 14 h; Inert atmosphere A mixture of compound 2 (6.2 g, 25 mmol), iodobenzene (6.12 g, 30 mmol), Cul (955 mg, 5.0 mmol), Cs2C03 (16.3 g, 50 mmol) in TEOS (200 ml) was degassed and purged with nitrogen. The resulting mixture was stirred at 140 ° C for 14 hrs. After cooling to r.t., the residue was diluted with EtOAc (200 ml). 95percent EtOH (200 ml) and H4F-H20 on silica gel [50g, pre-prepared by the addition of H4F (lOOg) in water (1500 ml) to silica gel (500g, 100-200 mesh)] was added, and the resulting mixture was kept at r.t. for 2 hrs. The solidified materials were filtered and washed with EtOAc. The filtrate was evaporated to dryness and the residue was purified by silica gel chromatography (petroleum ethers/EtOAc = 10/1) to give a yellow solid (3 g, 38percent)
38% at 140℃; for 14 h; A mixture of compound 2 (6.2 g, 25 mmol), iodobenzene (6.12 g, 30 mmol), Cul (955 mg, 5.0 mmol), Cs2CO3 (16.3 g, 50 mmol) in TEOS (200 ml) was degassed and purged with nitrogen. The resulting mixture was stirred at 140 °C for 14 hrs. After cooling to r.t., the residue was diluted with EtOAc (200 ml). 95percent EtOH (200 ml) and H4F-H20 on silica gel [50 g, pre-prepared by the addition of H4F (100 g) in water (1500 ml) to silica gel (500 g, 100-200 mesh)] was added, and the resulting mixture was kept at r.t. for 2 hrs. The solidified materials were filtered and washed with EtOAc. The filtrate was evaporated to dryness and the residue was purified by silica gel chromatography (petroleum ether/EtOAc = 10/1) to give a yellow solid (3 g, 38percent).
38% at 140℃; for 14 h; Inert atmosphere 10282] A mixture of compound 2 (6.2 g, 25 mmol),iodobenzene (6.12 g, 30 mmol), Cul (955 mg, 5.0 mmol),Cs2CO3 (16.3 g, 50 mmol) in TEOS (200 ml) was degassedand purged with nitrogen. The resulting mixture was stirredat 1400 C. for 14 hrs. After cooling to r.t., the residue wasdiluted with EtOAc (200 ml). 95percent EtOH (200 ml) andNH4F—H20 on silica gel [50 g, pre-prepared by the addition of NH4F (100 g) in water (1500 ml) to silica gel (500g, 100-200 mesh)] was added, and the resulting mixture waskept at r.t. for 2 hrs. The solidified materials were filtered andwashed with EtOAc. The filtrate was evaporated to drynessand the residue was purified by silica gel chromatography(petroleum ethers/EtOAc10/1) to give a yellow solid (3 g,38percent).
38% at 140℃; for 14 h; Synthesis of Intermediate 3: A mixture of compound 2 (6.2 g, 25 mmol), iodobenzene (6.12 g, 30 mmol), Cul (955 mg, 5.0 mmol), Cs2C03 (16.3 g, 50 mmol) in TEOS (200 ml) was degassed and purged with nitrogen. The resulting mixture was stirred at 140 °C for 14 hrs. After cooling to r.t. , the residue was diluted with EtOAc (200 ml) . 95percent EtOH (200 ml) and NH4F-H20 on silica gel [50g, pre-prepared by the addition of NH4F (1 OOg) in water (1500 ml) to silica gel (500g, 100-200 mesh)] was added, and the resulting mixture was kept at r.t. for 2 hrs. The solidified materials were filtered and washed with EtOAc. The filtrate was evaporated to dryness and the residue was purified by silica gel chromatography (petroleum ethers/EtOAc = 10/1) to give a yellow solid (3 g, 38percent).
38% at 140℃; for 14 h; A mixture of compound 2 (6.2 g, 25 mmol), iodobenzene (6.12 g, 30 mmol), Cul (955 mg, 5.0 mmol), Cs2C03 (16.3 g, 50 mmol) in TEOS (200 ml) was degassed and purged with nitrogen. The resulting mixture was stirred at 140 °C for 14 hrs. After cooling to r.t., the residue was diluted with EtOAc (200 ml). 95percent EtOH (200 ml) and NH4F- H20 on silica gel [50g, pre-prepared by the addition of NH4F (100g) in water (1500 ml) to silica gel (500g, 100-200 mesh)] was added, and the resulting mixture was kept at r.t. for 2 hrs. The solidified materials were filtered and washed with EtOAc. The filtrate was evaporated to dryness and the residue was purified by silica gel chromatography (petroleum ethers/EtOAc = 10/1) to give a yellow solid (3 g, 38percent).
38% at 140℃; for 14 h; Inert atmosphere A mixture of compound 2 (6.2 g, 25 mmol), iodobenzene (6.12 g, 30 mmol), Cul (955 mg, 5.0 mmol), Cs2C03 (16.3 g, 50 mmol) in TEOS (200 ml) was degassed and purged with nitrogen. The resulting mixture was stirred at 140 °C for 14 hrs. After cooling to r.t., the residue was diluted with EtOAc (200 ml). 95percent EtOH (200 ml) and NH4F- H20 on silica gel [50g, pre-prepared by the addition of NH4F (100g) in water (1500 ml) to silica gel (500g, 100-200 mesh)] was added, and the resulting mixture was kept at r.t. for 2 hrs. The solidified materials were filtered and washed with EtOAc. The filtrate was evaporated to dryness and the residue was purified by silica gel chromatography (petroleum ethers/EtOAc = 10/1) to give a yellow solid (3 g, 38percent).
38% at 140℃; for 14 h; Inert atmosphere A mixture of compound 2 (6.2 g, 25 mmol), iodobenzene (6.12 g, 30 mmol), Cul (955 mg, 5.0 mmol), Cs2C03 (16.3 g, 50 mmol) in TEOS (200 ml) was degassed and purged with nitrogen. The resulting mixture was stirred at 140 °C for 14 hrs. After cooling to r.t., the residue was diluted with EtOAc (200 ml). 95percent EtOH (200 ml) and NH4F- H20 on silica gel [50g, pre-prepared by the addition of NH4F (100g) in water (1500 ml) to silica gel (500g, 100-200 mesh)] was added, and the resulting mixture was kept at r.t. for 2 hrs. The solidified materials were filtered and washed with EtOAc. The filtrate was evaporated to dryness and the residue was purified by silica gel chromatography (petroleum ethers/EtOAc = 10/1) to give a yellow solid (3 g, 38percent).
38% at 140℃; for 14 h; Inert atmosphere A mixture of compound 2 (6.2 g, 25 mmol), iodobenzene (6.12 g, 30 mmol), Cul (955 mg, 5.0 mmcl), Cs2CO3 (16.3 g, 50 mmcl) in TEOS (200 ml) wasdegassed and purged with nitrogen. The resulting mixture was stirred at 140 9C for 14 hrs.After cooling to r.t., the residue was diluted with EtOAc (200 ml). 95percent EtCH (200 ml) andNH4F-H20 on silica gel [50g, pre-prepared by the addition of NH4F (1 OOg) in water (1500 ml)to silica gel (500g, 100-200 mesh)] was added, and the resulting mixture was kept at r.t. for 2 hrs. The solidified materials were filtered and washed with EtOAc. The filtrate was evaporated to dryness and the residue was purified by silica gel chromatography (petroleum ethers/EtOAc = 10/1) to give a yellow solid (3 g, 38percent).

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