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CAS No. : | 591-18-4 |
Formula : | C6H4BrI |
M.W : | 282.90 |
SMILES Code : | C1=C(C=CC=C1Br)I |
MDL No. : | MFCD00001043 |
InChI Key : | CTPUUDQIXKUAMO-UHFFFAOYSA-N |
Pubchem ID : | 11561 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; for 24h;Heating / reflux; | 2- A. Production of compound 2a; [79] After l-bromo-3-iodobenzene (10 g, 35.35 mmol) and 2-naphthalene bromic acid(5.47 g, 31.82 mmol) were dissolved in anhydrous THF (100 mL), Pd(PPh ) (1.2 g, 1.06 mmol) and 50 mL of 2M K CO aqueous solution were added and then refluxed <n="17"/>for 24 hours. The organic layer was extracted by using ethyl acetate and water was removed with magnesium sulfate. The organic layer was filtered at reduced pressure and concentrated, and the solvent was removed. The resulting substance was purified by using column chromatography and then recrystallized in THF and ethanol to obtain a white solid compound 2a (8.5 g, 85%).[80] MS [M + H] = 283 |
76% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; toluene; for 24h;Inert atmosphere; Reflux; | Under an argon gas atmosphere, 243 g (1.41 mol) of 2-naphthaleneboronic acid, 400 g (1.41 mol) of 3-bromoiodobenzene, 3.27 g (28.2 mmol) of tetrakis(triphenylphosphine)palladium(0), 6.4 L of toluene and 3.2 L of aqueous solution of 2M sodium carbonate were added together, and stirred while being refluxed for 24 hours. After the reaction was over, the mixture experienced filtration, through which aqueous phase thereof was eliminated. After organic phase thereof was washed by water and dried with magnesium sulfate, the toluene was distilled away under reduced pressure. Residue thereof was refined by silica-gel column chromatography, such that 303 g of 2-(3-bromophenyl)naphthalene was obtained at an yield of 76%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42% | lsobutylmagnesium bromide (2M in diethyl ether, 26.5ml, 53mmol) was added over 30 minutes at room temperature to a solution of 1-bromo-3-iodobenzene (1Og, 35.3mmol) and tetrakis(triphenylphosphine)palladium (0) (1.1 g, 0.954mmol) in toluene (160ml). The reaction mixture became green and the temperature was not allowed to rise above 400C. The reaction mixture was then stirred at room temperature for three hours. Aqueous ammonium chloride solution (160ml) was then added (the reaction became red) and the mixture was extracted with diethyl ether (2x100ml). The organics were washed with more ammonium chloride (100ml), dried over magnesium sulphate and concentrated under reduced pressure. The crude product was then purified by distillation to provide the title compound (boiling point 88C under 25mmHg, 3.2Og, 42%). 1H-NMR (400MHz, CDCI3) : delta = 0.90 (d, 6H), 1.85 (m, 1 H), 2.44 (d, 2H), 7.07 (d, 1 H), 7.14 (t, 1 H)1 7.30 (m, 2H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With palladium diacetate; sodium carbonate; triphenylphosphine; In water; toluene; for 7h;Inert atmosphere; Reflux; | 4,4,5,5-tetra-methyl-2-(triphenylene-2-yl) 1,3,2-dioxaborolan 7.08g (20.0mmol), m- bromoiodobenzene16.97g (60.0mmol) , palladium acetate 135 mg (0.60 mmol), triphenylphosphine629 mg (2.40 mmol), sodium carbonate 4.24 g (40.0 mmol), was mixed1,2-dimethoxyethane 100 mL, water 50 mL, under nitrogen atmosphere, 7 It washeated to reflux time. After the reaction, the organic layer was extracted byadding water and ethyl acetate. The organic layer was concentrated underreduced pressure, silica gel column chromatography (developing solvent:toluene) to remove origin ingredients. The solvent was evaporated under reducedpressure, and the resulting solid was dissolved in a small amount of methylenechloride, solid was precipitated with the addition of methanol. The solid wasfiltered, methanol, to give 7.33g of the synthetic intermediate 2 bysequentially washed with hexane (96% yield). |
95% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; toluene; for 8h;Reflux; Inert atmosphere; | (B-2) Synthesis of intermediate B Under an argon atmosphere, 3.54 g of triphenylene-2-boronic acid piconal ester, 2.83 g of 3-bromoiodebenzene, 0.231 g of tetrakis(triphenylphosphine)palladium (0), 40 mL of toluene and 20 mL of a 2M sodium carbonate aqueous solution were placed in a flask, and refluxed with stirring for 8 hours. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous phase was removed, and an organic phase was washed with water and saturated brine sequentially, and then dried with magnesium sulfate. Magnesium sulfate was filtered out, and then the organic phase was concentrated. The resulting residue was purified by means of a silica gel column chromatography to obtain 3.64 g (95%) of an intermediate B. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; diisopropylamine; In N,N-dimethyl-formamide; at 20℃; for 5h;Inert atmosphere; | General procedure: To a mixture of Pd(PPh3)2Cl2 (2 mol %), CuI (4 mol %) and DMF (15 mL) taken in a flask, aryl iodide (10 mmol), propiolic acid (12 mmol) and diisopropylamine (25 mmol) were added in that sequence under nitrogen atmosphere. After stirring the reaction mixture at room temperature for 5 h, the resulting mixture was diluted with ethyl acetate, filtered through celite bed, the filtrate was washed with cold aqueous KOH solution (1 × 100 mL) and acidified with dilute sulfuric acid (10% solution) at 0 C. The solid obtained was extracted with dichloromethane and the extract was washed with water, brine solution and dried over anhydrous sodium sulfate. The organic layer was concentrated in vacuo at 40 C, dried to get the arylpropiolic acid. Arylpropiolic acid (5 mmol) or 2-butynoic acid (5 mmol) was transferred into a 30 mL glass tube and then iodo compound (5 mmol), l-proline (15 mol %), cuprous bromide (5 mol %) and potassium carbonate (10 mmol) in DMSO or DMF (10 mL) were added in that order. The sealed tube was then subjected to a vacuum and refilled with nitrogen for five times under stirring at room temperature. The tube was placed in an oil bath and heated with stirring at 100 C for 3-5 h. After the reaction, the reaction mixture was mixed with ethyl acetate and washed with water, brine solution and dried over anhydrous sodium sulfate. Removal of the solvent in vacuo and purification of the residue by silica-gel column chromatography with hexane/ethyl acetate afforded the desired product. See Supplementary data for spectral data of all compounds. | |
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; diisopropylamine; In N,N-dimethyl-formamide; at 20℃; for 5h;Inert atmosphere; | General procedure: Compounds (1b-1o) were prepared according to literature.17 To a mixture of Pd(PPh3)2Cl2 (70 mg, 2 mol%), CuI (38 mg, 4 mol%) and DMF (7 mL) taken in a flask, aryl iodide (5.0 mmol), propiolic acid (414 mg, 6.0 mmol) and diisopropylamine (1.30 g, 12.5 mmol) were added in that sequence under nitrogen atmosphere. After stirring the reaction mixture at room temperature for 5 h, the resulting mixture was diluted with ethyl acetate, filtered through Celite bed, the filtrate was washed with cold aqueous KOH solution (1 x 100 mL) and acidified with dilute sulfuric acid (10% solution) at 0 C. The solid obtained was extracted with dichloromethane and the extract was washed with water, brine solution and dried over anhydrous sodium sulfate. The organic layer was concentrated in vacuum at 40 C, dried to get the arylpropiolic acids. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate; In hexane; dichloromethane; | Example 9 Synthesis of Carbazole Derivative 9 3,6-Diphenylcarbazole (2.80 g, 8.77 mmol), 1-bromo-3-iodobenzene (22.18 g, 87.7 mmol), copper powder (0.279 g) and potassium carbonate (4.85 g) were mixed together, and the mixture was heated in a nitrogen atmosphere at 190° C. for 9 hours. The resultant mixture was cooled to room temperature and diluted with methylene chloride, followed by washing with water and drying, to thereby obtain a pale brown liquid. Next, the obtained liquid is purified through silica gel column chromatography using a solvent mixture of methylene chloride/hexane (2/3 by volume), to thereby obtain 3.59 g of 9-(3-bromophenyl)-<strong>[56525-79-2]3,6-diphenylcarbazole</strong>. | |
3.59 g | With copper; potassium carbonate; at 190℃; for 9h;Inert atmosphere; | 3,6-Diphenylcarbazole (2.80 g, 8.77 mmol), 1-bromo-3-iodobenzene (22.18 g, 87.7 mmol), copper powder (0.279 g) and potassium carbonate (4.85 g) were mixed together, and the mixture was heated in a nitrogen atmosphere at 190° C. for 9 hours. The resultant mixture was cooled to room temperature and diluted with methylene chloride, followed by washing with water and drying, to thereby obtain a pale brown liquid. Next, the obtained liquid is purified through silica gel column chromatography using a solvent mixture of methylene chloride/hexane (2/3 by volume), to thereby obtain 3.59 g of 9-(3-bromophenyl)-<strong>[56525-79-2]3,6-diphenylcarbazole</strong>. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In toluene; at 90℃; for 48h;Inert atmosphere; | 1-bromo-3-iodobenzene (2.0g, 7.07mmol), <strong>[890042-13-4]4,4,5,5-tetramethyl-2-(triphenylen-2-yl)-1,3,2-dioxaborolane</strong> (2.5g, 7.07mmol), tetrakis(triphenylphosphine)palladium(0) (0.25g, 0.21mmol), and 1M Na2CO3 (35.4ml) in 100ml of toluene was stirred at 90C for 48h under nitrogen atmosphere. To the reaction mixture was added a dibenzo[b,d]thiophene-4-ylboronic acid (1.61g, 7.07mmol) and then stirred at 120C for 24h under nitrogen atmosphere. After the reaction had finished, the mixture was washed three times with distilled water and extracted with chloroform. The organic layer was separated, dried over anhydrous magnesium sulfate, and evaporated under reduced pressure. The crude product was purified by silica gel column chromatography using n-hexane-tetrahydrofuran (5:1). The final product was obtained as a white powder after purification by vacuum sublimation at a synthetic yield of 46%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With palladium diacetate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; sodium t-butanolate; In toluene; at 100℃; for 12.0h;Inert atmosphere; | General procedure: General procedure for the palladium-catalyzed reaction A solution of Pd(OAc)2 (0.8 mg, 0.0036 mmol), Xantphos (2.1 mg, 0.0036 mmol), NaOtBu (51 mg, 0.53 mmol), 1-bromo-4-iodobenzene (1a) (100 mg, 0.35 mmol), and N,N-diphenylamine (2a) (72 mg, 0.43 mmol) in toluene (0.5 mL) was stirred at 100 C for 12 h. The reaction was quenched with H2O, and extracted with CH2Cl2 (3*3 mL). The chemoselectivity (3aa/4aa=92/8) was measured by HPLC analysis using Inertsil ODS-3V. The pure monoaminated product 3aa (99 mg, 86%) was obtained by flash chromatography (hexane/CH2Cl2=97/3) as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; at 80℃; for 12h;Inert atmosphere; | Nitrogen environment in the compound I-8 (50 g, 140 mmol) and tetrahydrofuran (THF) 0.45 L dissolved after, here in 1-bromo-3-iodobenzene (43.7 g, 154 mmol) and tetrakis (triphenylphosphine) palladium (1.62 g and stirred into a 1.40 mmol). Into the potassuim carbonate (48.4 g, 350 mmol) in saturated water it was heated to reflux at 80 for 12 hours. After the reaction was completed, the reaction solution into water and extracted with dichloromethane (DCM), and then removing water by anhydrous MgSO4 One was then filter, and concentrate under reduced pressure. The obtained residue was purified by flash column chromatography to give the compound I-15 (41.5 g, 77%). |
77% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 10h;Reflux; Inert atmosphere; | 196.48 mmol) of Intermediate L-5, 72.26 g (255.42 mmol) of 1-bromo-3-iodebenzene, 54.31 g (392.96 mmol) of potassium carbonate, Pd (PPh3) ) Was added to 400 mL of tetrahydrofuran and 200 mL of water, and the mixture was heated under reflux for 10 hours under a nitrogen stream. The resulting mixture was added to 1500 mL of methanol, and the crystallized solid was filtered, and then dichloromethane was dissolved. The mixture was filtered through silica gel / celite, and an organic solvent was removed in an appropriate amount. The residue was recrystallized from methanol to obtain 3-bromo-5'-phenyl The yield of compound 3-bromo-5'-phenyl-1,1 ': 3,1 "-terphenyl (58.63 g, 77% The results of the analysis are as follows. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With potassium tert-butylate; palladium diacetate; tri tert-butylphosphoniumtetrafluoroborate; In toluene; for 24h;Inert atmosphere; Reflux; | To the reaction flask was added Intermediate 18-4 (10g, 35.3mmol), m-bromo-iodobenzene (12g, 42mmol), potassium tert-butoxide (7.9g, 70.6mmol), palladium acetate (0.3g, 1.3mmol), tri-tert-butylphosphine tetrafluoroborate (0.8g, 2.7mmol) and toluene (150 mL), under nitrogen was heated at reflux for 24 hours, cooled, toluene was removed, dichloromethane was added, washed with water, dried, the crude product by column to give 11g product, yield 71%. |
71% | With potassium tert-butylate; palladium diacetate; tri tert-butylphosphoniumtetrafluoroborate; In toluene; for 24h;Reflux; Inert atmosphere; | To the reaction flask was added 5,7-dihydro-7,7-dimethyl-indolo[2,1-b]carbazole (10 g, 35.3 mmol), m-bromoiodobenzene (12 g, 42 mmol) , potassium tert-butoxide (7.9 g, 70.6 mmol), palladium acetate (0.3 g), tri-tert-butylphosphine tetrafluoroborate (0.8 g) and toluene (150 mL), heated under reflux for 24 hours under nitrogen and cooled. Remove toluene, add dichloromethane, wash with water,Dry and the crude product was passed through a column to give 11 g of product, yield 71%. |
71% | With potassium tert-butylate; palladium diacetate; tri tert-butylphosphoniumtetrafluoroborate; In toluene; for 24h;Reflux; Inert atmosphere; | To the reaction flask was added 5,7-dihydro-7,7-dimethyl-indolo[2,1-b]carbazole (10 g, 35.3 mmol),M-bromoiodobenzene (12 g, 42 mmol), potassium t-butoxide (7.9 g, 70.6 mmol), palladium acetate (0.3 g),Tri-tert-butylphosphine tetrafluoroborate(0.8g) and toluene (150mL), heated under reflux for 24 hours under nitrogen, cooled, toluene removed,Add dichloromethane, wash with water, dry, and pass the crude product through the column.11 g of product was obtained in a yield of 71%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In 1,4-dioxane; water; at 100℃; for 2h; | A mixture of <strong>[57002-01-4](E)-(2-cyclohexylvinyl)boronic acid</strong> (0.657 g, 4.27 mmol), 1 -bromo-3- iodobenzene (0.518 mL, 4.06 mmol), tetrakis (0.235 g, 0.203 mmol), and sodium carbonate 10% wt. in water (12.93 g, 12.19 mmol) in 1 ,4-dioxane (20 mL) was stirred for 2.0 hours at 100C, the LCMS showed a complete reaction with a major product (the product did not show desired mass). After cooled to the room temperature, the mixture was diluted with water and extracted with ethyl acetate. The organic extract was dried over anhydrous magnesium sulfate. It was filtered and the filtrate was concentrated. The crude product was purified on the Combiflash eluting with 100% hexanes. The title compound was obtained as clear colorless oil (1 .0 g, 3.77 mmol, 93 % yield). 1H NMR (400 MHz, chloroform-d) delta ppm 1 .13 - 1 .41 (m, 5 H) 1 .71 (m, 1 H) 1 .80 (m, 4 H) 2.10 - 2.20 (m, 1 H) 6.16 - 6.25 (m, 1 H) 6.25 - 6.33 (m, 1 H) 7.12 - 7.21 (m, 1 H) 7.26 (d, J=7.78 Hz, 1 H) 7.32 (d, J=7.78 Hz, 1 H) 7.52 (s, 1 H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 100℃; for 18h;Inert atmosphere; | Intermediate I-37 (90 g, 329 mmol) was dissolved in toluene (1.0 L) in a nitrogen atmosphere,Here, 1-bromo-3-iodobenzene purchased from the tokyo chemical industry(102 g, 362 mmol), tris (diphenylideneacetone) dipalladium (0) (9.04 g, 9.87 mmol) tris-tert butylphosphine (9.98 g, 49.4 mmol) and sodium tert-butoxide(37.9 g, 395 mmol) were successively added thereto, followed by heating at 100 for 18 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM)The water was removed with MgSO4, filtered and concentrated under reduced pressure. The thus obtained residueFlash column chromatography to obtain Intermediate I-38 (95.8 g, 68%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With potassium phosphate; copper(l) iodide; In 1,4-dioxane; at 90℃; for 15h;Inert atmosphere; | Under a nitrogen atmosphere (N2 purging), Compound 1G(10 g, 35.48 mmol), 0.6 equivalent of Compound 3A, 0.1 equivalent of CuI, 3.5 equivalents of diaminocyclohexane, and 4.0 equivalents of potassium phosphate were added to 1,4-dioxane(350 ml), and stirred in a 90 C. oil bath. After 15 hours, water was added to the reaction mixture, and extraction was performed. Then, purification was performed using a column using a developing solvent of hexane: MC (3:2) to obtain a white solid 3B(12.93 g. yield 75%). |
With potassium phosphate; copper(l) iodide; In 1,4-dioxane; at 90℃; for 12h; | In a nitrogen environment and (N2 purging) 5A,0.6 equivalent of 2A, 0.1 equivalent of CuI,3.5 equivalents of diaminocyclohexane,4.0 equivalents of potassium phosphate are added to 1,4-dioxane and stirred in an oil bath at 90 C. Water was added to the reaction mixture after 12 hours, and after extraction with hexane: MC (4: 1) developing solvent, white solid 6A was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With tetrakis(triphenylphosphine) palladium(0); silver carbonate; In tetrahydrofuran; at 100℃; for 12h;Sealed tube; | Boronate ester (2.00 g, 5.40 mmol), 3-Bromoiodobenzene (1.38 mL, 10.8 mmol),Tetrakis (triphenylphosphine) palladium (0) (0.630 g, 0.540 mmol), Ag 2 CO 3 (2.99 g, 10.8 mmol) and 90 mL of tetrahydrofuran were placed in a 150 mL medium pressure vessel.The mixture was heated and stirred for 12 hours at 100 .The reaction solution was cooled to room temperature,Filtered through celite.The filtrate was concentrated in vacuo,The residue was purified by column chromatography (Hexane: Toluene = 4: 1)Thus,43-2 (9- (3'-bromo- [1,1'-biphenyl] -3-yl) -9H-carbazole) (1.61 g, 75% yield). |