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CAS No. : | 1190360-23-6 | MDL No. : | MFCD28955974 |
Formula : | C15H13Br | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | VECLPBKDHAALGQ-UHFFFAOYSA-N |
M.W : | 273.17 | Pubchem ID : | 59629661 |
Synonyms : |
|
Num. heavy atoms : | 16 |
Num. arom. heavy atoms : | 12 |
Fraction Csp3 : | 0.2 |
Num. rotatable bonds : | 0 |
Num. H-bond acceptors : | 0.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 72.09 |
TPSA : | 0.0 Ų |
GI absorption : | Low |
BBB permeant : | No |
P-gp substrate : | Yes |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | Yes |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -4.34 cm/s |
Log Po/w (iLOGP) : | 3.06 |
Log Po/w (XLOGP3) : | 5.11 |
Log Po/w (WLOGP) : | 4.76 |
Log Po/w (MLOGP) : | 4.92 |
Log Po/w (SILICOS-IT) : | 5.16 |
Consensus Log Po/w : | 4.6 |
Lipinski : | 1.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -5.31 |
Solubility : | 0.00134 mg/ml ; 0.00000492 mol/l |
Class : | Moderately soluble |
Log S (Ali) : | -4.85 |
Solubility : | 0.00382 mg/ml ; 0.000014 mol/l |
Class : | Moderately soluble |
Log S (SILICOS-IT) : | -6.8 |
Solubility : | 0.0000432 mg/ml ; 0.000000158 mol/l |
Class : | Poorly soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 2.51 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319 | Packing Group: | N/A |
GHS Pictogram: |
* 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 |
---|---|---|
96% | With sodium t-butanolate In dimethyl sulfoxide at 80 - 90℃; for 0.5 h; | 37 g (152 mmol) of 3-bromo-9H-fluorene are dissolved in 600 ml of dry DMSO in a flask dried by heating. 43.9 g (457 mmol) of NaOtBu are added at room temperature. Let the blue suspension now have an internal temperature of 80 ° C. At this temperature, 64.8 g (457 mmol) of iodomethane are added dropwise to the purplish solution at a rate that does not exceed an internal temperature of 90 deg. C (duration: about 30 minutes). The batch is kept at an internal temperature of 80-90 ° C for an additional 30 minutes, then poured into 1500 ml of ice water and stirred for about 20 minutes. The precipitated solid is filtered off with suction and washed successively with about 200 ml of H2O and methanol. Yield: 39 g (144 mmol), 96percent of theory; Purity: 95percent by'H-NMR. |
95% | With sodium t-butanolate In dimethyl sulfoxide at 20 - 65℃; for 1 h; | 29.5 g (120 millimol) of 3-bromo-9H-fluorene (Tetrahedron Letters, 51, 37, 4894-4897; 2010) is dissolved in 220 ml of anhydrous DMSO in the flask dried by heating. 34.7 g (361 millimol) NaOt Bu is added at room temperature. Suspension is made into the internal temperature of 65 degrees C. 22.5 ml (361 millimol) iodomethane solution in DMSO (50 ml) was added at this internal temperature which does not exceed 65 degrees C (period: for about 30 minutes). A batch is maintained with the degree of internal temperature of 65 degrees C for further 30 minutes. Then, it flows into the 400-ml well cold aqueous Na4OH solution (1/1, v/v), and stirred for about 20 minutes. Suction filtration of the precipitating solid is carried out, and washed continuously with about 200 ml of H2O and methanol. Yield: 31g (114 millimol) (95percent of a theoretical value). |
65 mmol | With potassium <i>tert</i>-butylate In dimethyl sulfoxide at 80 - 90℃; | (6) take the product 70mmol, add solvent DMSO, potassium tert-butanol 280mmol,80 degrees Celsius stirring 1h. Dropping methyl iodide 280 mmol,The temperature was raised to 90 ° C and the reaction was carried out overnight to obtain 65 mmol of product. |
30 g | With potassium <i>tert</i>-butylate In dimethyl sulfoxide at 80 - 90℃; for 0.5 h; | A mixture of 37 g (152 mmol) of 17-0Was dissolved in 600 ml of DMSO at room temperature,43.9 g (457 mmol) of potassium t-butoxide was added and the temperature was raised to 80 ° C.64.8 g (457 mmol) of methyl iodide was added dropwise to control the temperature not to exceed 90 ° C.At 80-90 ° C for 30 min, add 1000 ml of water, stir,The precipitated solid was washed with water and methanol. To obtain product 17-1 30g. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | Stage #1: at 0 - 20℃; for 3 h; Inert atmosphere Stage #2: With hydrogenchloride; acetic acid In water for 10 h; Reflux |
Add (15 g, 52 mmol) and 100 mL of tetrahydrofuran in a dry 300 mL round-bottom flask reactor under nitrogen atmosphere and add methylmagnesium bromide (10 mL, 300 mmol) dropwise at 0 ° C.After completion of dropwise addition, the mixture is stirred at room temperature for 3 hours.After completion of the reaction, add 100 mL of 2 N HCl aqueous solution at 0 ° C and stir for 30 minutes.The layers were separated with ethyl acetate, and the organic layer was concentrated. Immediately, 100 mL of acetic acid and 10 mL of hydrochloric acid were added, and the mixture was refluxed with stirring for 10 hours.After completion of the reaction, an excess amount of water was added, and the mixture was stirred for 30 minutes, and then filtered. The resultant was separated by column chromatography to obtain (12.1 g, 86percent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With lithium amide; potassium tert-butylate;tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium(0); In hexane; xylene; at 20℃; for 6h;Inert atmosphere; Reflux; | Example 1[0060]Synthesis of Exemplified compound A1[0061][Chem. 5][0062]Exemplified compound A1 represented by this formula was synthesized in the following manner. A 100 ml three-neck flask was prepared and charged with 0.40 g (1.46 mmol) of 3-bromofluorene, 0.35 g (14.6 mmol) of lithium amide (product name: lithium amide, manufactured by KISHIDA CHEMICAL Co., Ltd.), 0.49 g (5.0 mmol) of sodium tertiary butoxide (product name: sodium tertiary butoxide, manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.); further, 20 ml of xylene; while the solution was stirred at room temperature in a nitrogen atmosphere, 0.5 ml (0.15 mmol) of tri-tertiary-butylphosphine (10 wt% hexane solution); and then 0.67 mg (0.153 mmol) of palladium dibenzylideneacetone (product name: palladium dibenzylideneacetone, manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.). The flask was purged with argon and then the solution in the flask was stirred to reflux for 6 hours. After the reaction was complete, an organic layer was washed with water, dried over anhydrous sodium sulfate, and then purified with a silica gel column (developing solvent mixture of heptane and toluene) to provide 0.14 g (yield: 50.0%) of Exemplified compound A1 (white crystals).[0063]This compound was analyzed by MALDI-TOF MS (matrix assisted ionization time-of-flight mass spectrometry) and M+ of Exemplified compound A1, which is 593.0, was confirmed.[0064]Exemplified compound A1 was subjected to 1H-NMR measurement with an ECA-400 manufactured by JEOL Ltd. (solvent: deuterochloroform) and the delta values (ppm) thereof were found to be 7.56 (2H, dt), 7.42 (1H, dd), 7.32-7.25 (3H, m), 7.10 (1H, dd), and 1.52(6H, s).[0065]The band gap of Exemplified compound A1 was determined from an ultraviolet-visible light absorption spectrum and it was found to be 3.02 eV. In this specification, each band gap was determined with a spectrophotometer U-3010 manufactured by Hitachi, Ltd. from absorption ends of a thin film formed on a glass substrate.[0066]The ionization potential of Exemplified compound A1 was determined with an atmospheric photoelectron spectrometer (measurement apparatus name: AC-1, manufactured by Riken Keiki Co., Ltd.) and it was found to be 5.51 eV.[0067]The Tg of Exemplified compound A1 was measured with a Pyris 1 (manufactured by PerkinElmer, Inc.) and it was found to be 154degree(Celsius). Thus, Exemplified compound A1 had a high thermal stability.[0068]Exemplified compound A1 was further evaluated in terms of amorphousness.[0069]A chloroform solution of Exemplified compound A1 was prepared such that the concentration of Exemplified compound A1 was 0.1 wt%. This solution was dropped onto a glass substrate and spin-coating was performed to form a thin film. After that, the thin film was dried with a vacuum oven at 80degree(Celsius) for 10 minutes to remove the solvent in the thin film.[0070]The resultant substrate was left in the oven at 60degree(Celsius) for a week. Then, the occurrence of crystallization in the film was visually inspected and it was confirmed that no crystallization occurred. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; for 5h;Inert atmosphere; Reflux; | The following reagents and solvents were loaded in a 100-ml recovery flask. CRY-2: 1.23 g (3.0 mmol) NP-2: 0.53 g (3.1 mmol) Tetrakis (triphenylphosphine) palladium (0) : 0.1 g (0.08 mmol) Toluene: 10 ml Ethanol: 5 ml 10 wt% sodium . carbonate aqueous solution: 5 ml Next, under nitrogen, the reaction solution was heated to reflux for 5 hours while being stirred. After the completion of the reaction, the reaction solution was washed with water and then dried with sodium sulfate, followed by concentration under reduced pressure. Thus, a crude product was obtained. Next, the crude product was purified by silica gel column chromatography (developing solvent: toluene/heptane=2/l ) to provide 0.99 g of NPCRY-1 (yield: 85%). Exemplified Compound X-lll was obtained by the same method as that of Synthesis Example 6 except that in Synthesis Example 6, FL-3 shown below was used instead of CRY-2 and NPTRP-1 was used instead of NP-2. The resultant compound was evaluated for its purity by employing HPLC. As a result, it was confirmed that the purity was 99% or more. MALDI-TOF MS confirmed that the compound had an M+ of 546.2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With copper; potassium carbonate; In nitrobenzene; at 210℃; for 12h;Inert atmosphere; | A stream of nitrogen 2-(1H-indol-5-yl)-9-phenyl-9H-carbazole (118.1g, 329.4mmol), <strong>[1190360-23-6]3-bromo-9,9-dimethyl-9H-fluorene</strong> (108.0 g, 395.3 mmol) , Cu (10.5 g, 164.7 mmol), K2CO3 (91.1 g, 658.8 mmol) and nitrobenzene (2000 ml) and stirred for 12 hours at 210C . After the reaction terminated, the reaction mixture extracted with ethyl acetateRemoving water over MgSO4, purified by column chromatography Hexane EA = 6 1 (v / v)) to yield 2-(1-(9, 9-dimethyl-9H-fluoren-3-yl)-1H-indol-5-yl)-9-phenyl-9H-carbazole (146.9 g, a yield of 81%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With copper; potassium carbonate; In nitrobenzene; at 210℃; for 12h;Inert atmosphere; | A stream of nitrogen 3-(1H-indol-5-yl)-9-phenyl-9H-carbazole (127.5g, 355.7mmol), <strong>[1190360-23-6]3-bromo-9,9-dimethyl-9H-fluorene</strong> (116.6 g, 426.9 mmol) , Cu (11.3 g, 177.9 mmol), K2CO3 (98.3 g, 711.5 mmol) and nitrobenzene (2000 ml) and stirred for 12 hours at 210C . After the reaction terminated, the reaction mixture extracted with ethyl acetateRemoving water over MgSO4, purified by column chromatography Hexane EA = 6 1 (v / v)) to yield 3-(1-(9, 9-dimethyl-9H-fluoren-3-yl)-1H-indol-5-yl)-9-phenyl-9H-carbazole (156.7 g, a yield of 80%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With copper; potassium carbonate; In nitrobenzene; at 210℃; for 12h;Inert atmosphere; | A stream of nitrogen 5-(dibenzo[b,d]furan-4-yl)-1H-indole (94.6 g, 333.8 mmol), <strong>[1190360-23-6]3-bromo-9,9-dimethyl-9H-fluorene</strong> (109.4 g, 400.5 mmol) , Cu (10.6 g, 166.9 mmol), K2CO3 (92.3 g, 667.6 mmol) and nitrobenzene (2000 ml) and stirred for 12 hours at 210C . After the reaction terminated, the reaction mixture extracted with ethyl acetateRemoving water over MgSO4, purified by column chromatography Hexane EA = 6 1 (v / v)) to yield 5-(dibenzo[b,d]furan-4-yl)-1-(9,9-dimethyl-9H-fluoren-3-yl)-1H-indole(117.5 g, a yield of 74%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With sodium t-butanolate; In dimethyl sulfoxide; at 80 - 90℃; for 0.5h; | 37 g (152 mmol) of 3-bromo-9H-fluorene are dissolved in 600 ml of dry DMSO in a flask dried by heating. 43.9 g (457 mmol) of NaOtBu are added at room temperature. Let the blue suspension now have an internal temperature of 80 C. At this temperature, 64.8 g (457 mmol) of iodomethane are added dropwise to the purplish solution at a rate that does not exceed an internal temperature of 90 deg. C (duration: about 30 minutes). The batch is kept at an internal temperature of 80-90 C for an additional 30 minutes, then poured into 1500 ml of ice water and stirred for about 20 minutes. The precipitated solid is filtered off with suction and washed successively with about 200 ml of H2O and methanol. Yield: 39 g (144 mmol), 96% of theory; Purity: 95% by'H-NMR. |
95% | With sodium t-butanolate; In dimethyl sulfoxide; at 20 - 65℃; for 1h; | 29.5 g (120 millimol) of 3-bromo-9H-fluorene (Tetrahedron Letters, 51, 37, 4894-4897; 2010) is dissolved in 220 ml of anhydrous DMSO in the flask dried by heating. 34.7 g (361 millimol) NaOt Bu is added at room temperature. Suspension is made into the internal temperature of 65 degrees C. 22.5 ml (361 millimol) iodomethane solution in DMSO (50 ml) was added at this internal temperature which does not exceed 65 degrees C (period: for about 30 minutes). A batch is maintained with the degree of internal temperature of 65 degrees C for further 30 minutes. Then, it flows into the 400-ml well cold aqueous Na4OH solution (1/1, v/v), and stirred for about 20 minutes. Suction filtration of the precipitating solid is carried out, and washed continuously with about 200 ml of H2O and methanol. Yield: 31g (114 millimol) (95% of a theoretical value). |
85.3% | With sodium t-butanolate; In tetrahydrofuran; for 6h;Inert atmosphere; | To a 250 mL two-neck round bottom flask (nitrogen)Joining one after another1 g of 3-bromo-9H-fluorene (4.08 mmol),2.3 g sodium tert-butoxide (24.1 mmol)And 100 mL of anhydrous tetrahydrofuran,Stir well and add 2.3 g of methyl iodide (16.2 mmol)Reaction for 6 h. After the 3-bromo-9H-fluorene is completely consumed,Quench the reaction by adding 5 mL of water and adding 100 mL of dichloromethane.After extraction twice, the organic phase was concentrated to give a crude material.The crude product was purified by column chromatography to yield 0.95 g.Yield: 85.3%. MS (EI) m/z: 272.54 [M+]. |
65 mmol | With potassium tert-butylate; In dimethyl sulfoxide; at 80 - 90℃; | (6) take the product 70mmol, add solvent DMSO, potassium tert-butanol 280mmol,80 degrees Celsius stirring 1h. Dropping methyl iodide 280 mmol,The temperature was raised to 90 C and the reaction was carried out overnight to obtain 65 mmol of product. |
30 g | With potassium tert-butylate; In dimethyl sulfoxide; at 80 - 90℃; for 0.5h; | A mixture of 37 g (152 mmol) of 17-0Was dissolved in 600 ml of DMSO at room temperature,43.9 g (457 mmol) of potassium t-butoxide was added and the temperature was raised to 80 C.64.8 g (457 mmol) of methyl iodide was added dropwise to control the temperature not to exceed 90 C.At 80-90 C for 30 min, add 1000 ml of water, stir,The precipitated solid was washed with water and methanol. To obtain product 17-1 30g. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; for 5h;Inert atmosphere; Heating; | 30 g of biphenyl-3-yl-biphenyl-4-ylamine (93.4 millimol) and 25.5 g of <strong>[1190360-23-6]3-bromo-9,9-dimethyl-9H-fluorene</strong> (93.4 millimol) are dissolved in 600 ml of toluene, and solution was degassed, and saturated with N2. 3.2 g (3.73 millimol) of tri-tert-butylphosphine, and 0.42 g (1.87 millimol) palladium acetate (II). 13.9 g of sodium tert-butoxide (140 millimol) are added. Under a protective atmosphere, a reaction mixture is boiled and heated for 5 hours. Then, the mixture between toluene and water is fractionated, organic phase was washed 3 times with water, dried by Na2SO4, and evaporated in a rotarry evaporator. After filtering a crude product with toluene, the left-behind residue is made to recrystallize from heptane/toluene, and is made to sublimate in a high vacuum. Purity is 99.9%. Yield is 37.8g (79% of a theoretical value). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80 mmol | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In toluene; for 24h;Reflux; Inert atmosphere; | 100 mmol of the compound 11-a and 220 mmol of <strong>[1190360-23-6]3-bromo-9,9-dimethylfluorene</strong> were dissolved in 1000 ml of toluene, 400 mmol of potassium carbonate and 2 mmol of catalyst Pd [P (C6H5) 3] 4 were added and the reaction was refluxed under nitrogen for 24 hours. After completion of the reaction, 500 ml of distilled water was added, cooled and filtered, extracted with methylene chloride, washed with brine, and the organic layer was separated. The organic solvent was removed by steaming, recrystallization from dichloromethane and ethanol, and drying in vacuo to give 80 mmol of product compound 11. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 4h;Inert atmosphere; Reflux; | SYNTHESIS EXAMPLE 16 Synthesis of Compound C-11 (0256) (0257) 3-bromofluorene (11.7 g, 42.83 mmol), bis-biphenyl-4-yl-amine (12.51 g, 38.94 mmol), and sodium t-butoxide (7.86 g, 81.76 mmol) were put, and toluene (155 ml) was added thereto to dissolve them. Pd(dba)2 (0.357 g, 0.39 mmol) and tri-tertiary-butylphosphine (0.236 g, 1.17 mmol) were sequentially added thereto, and the resulting mixture was refluxed and stirred under a nitrogen atmosphere for 4 hours. When the reaction was complete, toluene and distilled water were used for an extraction, an organic layer therefrom was dried with magnesium sulfate and filtered, and the filter solution was concentrated under a reduced pressure. Then, a product therefrom was purified with n-hexane/dichloromethane (8:2 of a volume ratio) through silica gel column chromatography to obtain a desired compound C-11 (17.2 g, 86%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | G (259 mmol) of <strong>[1190360-23-6]3-bromo-9,9-dimethyl-9H-fluorene</strong> was dissolved in 1500 ml of dry THF and 135 ml (337 mmol) of a 2.5 M solution of n-butyllithium in cyclohexane- Dropwise at 70 C, and after 1 hour, 37 ml of trimethylborate (336 mmol) is added dropwise. The mixture is allowed to come to room temperature over a period of 1 hour and the solvent is removed. According to 1 H-NMR, a homogeneous residue is utilized in the subsequent reaction without further purification. The yield is 55 g (230 mmol), corresponding to 90% of theory. | |
47 mmol | (7) 60 mmol of the product was dissolved in anhydrous THF,Cooling to -78 degrees Celsius, slowly dropping 180mmol of n-butyl lithium,Natural temperature to room temperature, the reaction overnight, the next day, adding 180mmol trimethyl borate,Stir for 2 h.Adding excess dilute hydrochloric acid to quenching the reaction, EA extraction,Dried and concentrated to give 47 mmol of product ii. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With 1,1'-bis-(diphenylphosphino)ferrocene; palladium diacetate; sodium t-butanolate; In toluene; for 18h;Inert atmosphere; | A mixture of 50 g (183 mmol) of <strong>[1190360-23-6]3-bromo-9,9-dimethyl-9H-fluorene</strong>, 20 ml (220 mmol) of aniline, 1.5 g (2.7 mmol) Of DPPF palladium (II) acetate and 45 g (486 mmol) Of sodium tert-butoxide in 1.5 l of toluene under a protective atmosphere Heat and boil for 18 hours. The mixture is then partitioned between toluene and water, the organic phase is washed three times with water, dried over Na2SO4 and evaporated in a rotary evaporator. The remaining residue is recrystallized from heptane / ethyl acetate. The yield is 31.2 g (110 mmol, 52%). Yield: 46 g (165 mmol), 78% of theory; Purity: 97% according to 1 H-NMR. |
76% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 100℃; for 24h; | Step 1: The reactor was charged with aniline (0.75 g, 8 mmol), 2-bromo-9,9-dimethyl-9H-indole (1.82 g, 6.67 mmol), Pd2(dba)3 (0.17 g, 0.2 mmol), P(t-Bu)3 (0.14, 0.67 mmol), NaOt-Bu (2.24 g, 20 mmol), 100 mL of toluene solution, reaction at 100C for 24 h, extraction of the organic phase with diethyl ether and water after completion of the reaction, organic layer with MgSO4 After drying and concentrating the organics, column chromatography and recrystallization gave Intermediate 2-1 (1.45 g, 76%). |
75% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 100℃; for 24h; | Step2: The reactor was charged with aniline (0.75g, 8mmol), 3-bromo-9,9dimethylhydrazine (1.82g, 6.6mmol), Pd2(dba)3 (0.17g, 0.2mmol). , P(t_Bu) 3 (0.14, 0.67 mmol), Na0t_Bu (2.24 g, 20 mmol), 100 mL of toluene solution, reaction at 100 C for 24 h, the organic phase was extracted with ether and water after the reaction was completed, and the organic layer was dried over MgS04. , Concentrate organics, column chromatography, recrystallization to give intermediate 1 -b (1.43 g, 75%) |
75% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 100℃; for 24h; | added to the reactor of aniline (0.75 g, 8 mmol), 3 - bromo - 9, 9 dimethylfluorene (1.82 g, 6 . 67 mmol), Pd2(Dba)3(0.17 G, 0.2 mmol), P (t - Bu)3(0.14, 0 . 67 Mmol), NaOt - Bu (2.24 g, 20 mmol), toluene solution 100 ml, 100 C reaction under the condition of 24 h, reaction after the end of the ether and the water extracts the organic phase, the organic layer using MgSO4Drying, concentration of the organic matter, column chromatography, recrystallization to obtain intermediate 1 - b (1.43 g, 75%). |
70% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene;Reflux; | In a round bottom flask,The above 3-bromo-9,9-diphenyl--9H- fluorene 10.0g,Aniline 3.8g,t-BuONa 5.3g,Pd2(dba)3 1.4g,(t-Bu) 3P 1.6 ml was dissolved in 150 ml of toluene, and stirred under reflux.The reaction was confirmed by thin layer chromatography (TLC), and after adding water, the reaction was completed.The organic layer was extracted with methyl cellulose (MC), and subjected to filtration under reduced pressure, followed by recrystallization.OP1 was obtained in 7.3 g (yield 70%).The following OP2 to OP5 were synthesized using the same method as the above OP1 using different starting materials. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61 mmol | The 72mmol dichlorophenylphosphine was dissolved in anhydrous THF,Cooling to -78 degrees Celsius,Slowly adding 2.5 equivalents of n-butyllithium,Reaction 2h,Add 2 equivalents of 17-1 THF solution.And then slowly heated to room temperature reaction 3h.After completion of the reaction,Into a large number of water, a white product precipitation, filtration, filter cake on the silica gel column to get 61mmol products 17-2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With aluminum (III) chloride; In dichloromethane; at 0 - 20℃; for 20h;Inert atmosphere; | Aluminium chloride (0.5g, 0.007mol) dissolved in dichloromethane was cooled to 0C then acetyl chloride (0.5g, 0.007mol) was added slowly in drop wise under nitrogen atmosphere. 3-Bromo-9,9-dimethyl-9H-fluorene (2g, 0.007mol) was dissolved in dichloromethane and charged at the same temperature. The reaction mixture was allowed to attain room temperature for 20h with stirring; then poured into ice cold water and set aside for separation of organic layer. The product was extracted in chloroform, dried over sodium sulphate and subjected to column chromatography in hexane/ethylacetate mixture (5:1) to obtain pure white solid (0.44g; yield 80%, 1) [13]. |
62.6% | With aluminum (III) chloride; In dichloromethane; at 0 - 20℃; for 20h;Inert atmosphere; | Aluminium chloride (0.5 g, 0.007 mol) dissolved in dichloromethanewas cooled to 0 C then acetyl chloride (0.5 g, 0.007 mol)added slowly in drop wise under nitrogen atmosphere.3-Bromo-9,9-dimethyl-9H-fluorene (2 g, 0.007 mol) was dissolvedin dichloromethane and charged at the same temperature.The reaction mixture was allowed to attain room temperature for20 h with stirring; then poured into ice cold water and set aside forseparation of organic layer. The product was extracted inchloroform, dried over sodium sulphate and subjected to columnchromatography in hexane/ethylacetate mixture (5:1) to obtainpure white solid (1.44 g; yield 62.6%, 1) [15]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In N,N-dimethyl-formamide; at 150℃; for 5h; | <strong>[1190360-23-6]3-bromo-9,9-dimethylfluorene</strong> (100 g, 366 mmol, purchased from Zengzhon HQ Material Co., Ltd. (http:// www.hqmat.coml)) was dissolved in dimethylforamide (DMF, 1.0 L) under a nitrogen environment, bis(pinacolato) diboron (112 g, 439 mmol) and (1,1?-bis(diphenylphos- phine)ferrocene)dichloropalladium (II) (2.99 g, 3.66 mmol), and potassium acetate (108 g, 1,098 mmol) were added thereto, and the mixture was heated and refluxed at 150 C. for 5 hours. When a reaction was complete, water was added to the reaction solution, and the mixture was filtered and dried in a vacuum oven. A residue obtained in this way was separated and purified through flash column chromatography to obtain Intermediate 1-3 (99.6 g, 85%).1HRMS (70 eV, EI+): m/z calcd for C21H251302:320.1948, found: 320.1Elemental Analysis: C, 79%; H, 8% |
79% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In N,N-dimethyl-formamide; at 120℃; | After <strong>[1190360-23-6]3-bromo-9,9-dimethyl-9H-fluorene</strong> (50.0 g, 183 mmol) was dissolved in DMF (700 mL),bis(pinacolato)diboron (51.1 g, 201 mmol), KOAc (53.9 g, 549 mmol),PdCl2(dppf) (4.02 g, 5.49 mmol) was added and stirred at 120 C.When the reaction is complete, DMF is removed by distillation, and extracted with CH2Cl2 and water.When extraction is complete, the organic layer is dried over MgSO4 and concentrated.Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 46.3 g (yield: 79%) of the product. |
78% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In N,N-dimethyl-formamide; at 120℃; | After dissolving <strong>[1190360-23-6]3-bromo-9,9-dimethyl-9H-fluorene</strong> (50.0 g, 183 mmol) in DMF (1 L), bis (pinacolato) diboron (51.1 g, 201 mmol),KOAc (53.9 g, 549 mmol),PdCl2(dppf) (4.02 g, 5.49 mmol) was added and stirred at 120 C. When the reaction is complete, DMF is removed by distillation, and extracted with CH2Cl2 and water.When extraction is complete, the organic layer is dried over MgSO4 and concentrated.Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 45.7 g (yield: 78%) of the product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; toluene; at 110℃; for 5h;Inert atmosphere; | 38.2 g of product Intermediate B obtained from Reaction Scheme 2 and 32.8 g 3-bromo-9,9'-dimethylhydrazine was added to a 1L three-necked flask. Add 450mL of toluene and 10mL of ethanol to dissolve, Pass nitrogen for 15 minutes and add 180 mL of K2CO3 (3.0 eq., Aqueous solution of 2M) was finally added with 2.8g of Pd(PPh3)4 (2mol%). The temperature was raised to 110C and the reaction was completed for 5 hours. Add activated carbon adsorption, After suction filtration, the solvent was removed by rotation, dried, and recrystallized from toluene and ethanol. 37.8 g of intermediate C are obtained (yield 72%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | (42 g, 154 mmol) was added to a dry 1 L round bottom flask reactor Dissolved in 420 mL of tetrahydrofuran in a nitrogen stream, and 1.6 M n-butyllithium (155 mL, 247 mmol) was slowly added dropwise with stirring at -78 C.When dropping is completed, stirring is continued for 1 hour and 30 minutes while maintaining the temperature at -78 C.Then trimethyl borate (30.8 g, 297 mmol)And the mixture is stirred at room temperature for 1 hour. After completion of the reaction, 200 mL of a 2N hydrochloric acid aqueous solution is added dropwise at room temperature, and the mixture is stirred for 30 minutes.The reaction mixture was then extracted with ethyl acetate and water. The organic layer was concentrated under reduced pressure and recrystallized to obtain (34 g, 93%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | Add (15 g, 52 mmol) and 100 mL of tetrahydrofuran in a dry 300 mL round-bottom flask reactor under nitrogen atmosphere and add methylmagnesium bromide (10 mL, 300 mmol) dropwise at 0 C.After completion of dropwise addition, the mixture is stirred at room temperature for 3 hours.After completion of the reaction, add 100 mL of 2 N HCl aqueous solution at 0 C and stir for 30 minutes.The layers were separated with ethyl acetate, and the organic layer was concentrated. Immediately, 100 mL of acetic acid and 10 mL of hydrochloric acid were added, and the mixture was refluxed with stirring for 10 hours.After completion of the reaction, an excess amount of water was added, and the mixture was stirred for 30 minutes, and then filtered. The resultant was separated by column chromatography to obtain (12.1 g, 86%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 24h; | <strong>[1190360-23-6]3-bromo-9,9-dimethyl-9H-fluorene</strong> (2 g, 7.4 mmol), aminobiphenyl (2.5 g, 4.8 mmol)sodium tert-butoxide (2.1 g, 22.2 mmol) and tris (dibenzylideneacetone) dipalladium (0) (0.2 g, 0.225 mmol) were dissolved in 50 ml of toluene. Tri-tert-butylphosphine (0.12 g, 0.6 mmol) was added thereto and stirred for 24 hours.After confirming with HPLC and LC-MASS, the reaction was terminated.After removal of the solvent, it was extracted with MC / H2O.column (EA: Hex = 1: 4) and reprecipitated with MC / hexane.Thereafter, the mixture was vacuum-dried to obtain a solid compound (2.2 g, yield = 82%). |
78% | With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; In toluene; at 110℃; for 10h;Inert atmosphere; | 2.73g (10mmol) of 3-bromo-9,9?-dimethylfluorene,1.69g (10mmol) of 4-aminobiphenyl, 0.18g (0.2mmol) of tris (dibenzylideneacetone) dipalladium, 0.08g (0.2mmol) of 2-biscyclohexylphosphine-2 ', 6'-di Methoxybiphenyl, 1.92 g (20 mmol) of sodium tert-butoxide and 30 mL of toluene were added to a 100 mL flask, heated to reflux temperature (110 C.) under a nitrogen atmosphere for 10 h, and the reaction system was cooled to room temperature. 30 mL of water was added to quench, the reaction solution was extracted three times with 50 mL of ethyl acetate, the organic phase was dried with 4 g of magnesium sulfate, filtered and the solvent was distilled off, the crude product was recrystallized twice with toluene to obtain 2.81 g of intermediate 2-1, yield 78%. |
3.52g | With tris-(dibenzylideneacetone)dipalladium(0); tert-butylphosphine; sodium t-butanolate; In toluene; at 100℃; for 24h; | Biphenyl-4-amine (3.00 g, 17.73 mmol), 2-Bromo-9,9-Dimethylfluorene (5.33 g,19.5 mmol), sodium tert-butoxide (7.89 g, 39.0 mmol), Tris (dibenzylideneacetone) dipalladium (0) (0.71 g,0.65 mmol) and tert-butylphosphine (0.10 g, 1.06 mmol) were dissolved in Toluene (130 mL)After completion of the reaction, toluene was removed, and dichloromethane and water were used for extraction.The residue was purified by silica gel column, and the solvent was distilled off under reduced pressure to obtain Compound A6 (3.52 g, 9.75 mmol). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; at 110℃; | 17 g (82 mmol, 1.0 eq.) of Intermediate-1 and 22.4 g (82 mmol, 1.0 eq.)3-Bromo-9,9'-dimethylhydrazine was added to a 2L three-neck flask, dissolved in 800 ml of toluene and 80 ml of ethanol, nitrogen was passed for 15 minutes, and 123 ml of 2M aqueous solution containing 34 g (246 mmol, 3.0 eq.) of K2CO3 was added. Finally, 1.9 g of Pd(PPh3)4 (2 mol %) was added.The temperature was raised to 110C and the reaction was completed overnight. Activated carbon adsorption was added, suction filtration, solvent removal, drying, recrystallization with toluene and ethanol, 23.6 g of Intermediate-2 was obtained with a yield of 81%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42.5% | With potassium phosphate; copper(l) iodide; In 5,5-dimethyl-1,3-cyclohexadiene; for 6h;Inert atmosphere; Reflux; | Under a nitrogen atmosphere, to a 500 ml three-neck flask, 78.3 g of compound Q (100 mmol) and 30.3 g of compound R were added.(110 mmol), 7.6 g of cuprous iodide (40 mmol), 42.4 g of tripotassium phosphate (200 mmol), and 300 g of xylene were heated and refluxed for 6 hours, and TLC traced no compound Q.After the reaction is complete, the temperature is reduced to 30 C., filtered, and the xylene 50 ml*3 is rinsed. The filtrate is washed with water 200 g*3 until pH=7. After drying, the silica gel column is subjected to atmospheric pressure. After the column is completed, xylene 50ml*2 is rinsed on the silica gel column, rinsed, and the eluent is passed over.The solvent was decompressed and the solvent was removed. The desolvent was recrystallized three times by adding 400 g of chloroform and 400 g of n-hexane. After drying, 41.5 g of compound 45 was obtained. Yield: 42.5%, HPLC: 99.5%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
5.35g | With tris-(dibenzylideneacetone)dipalladium(0); tert-butylphosphine; sodium t-butanolate; In toluene; at 80℃; for 24h; | To a 500 mL round bottom flask was added 4-Amino-p-terphenyl (5.00 g, 20.38 mmol), 2-Bromo-9,9-Dimethylfluorene(5.57 g, 32.50 mmol), sodium tert-butoxide (9.07 g, 44.84 mmol) Tris (dibenzylideneacetone) dipalladium (0)(0.75 g, 0.82 mmol) and tert-butylphosphine (0.12 g, 1.22 mmol) were dissolved in toluene (250 mL)In a bath at 80 CAfter stirring for 24 hours, after the reaction was completed, toluene was removed, and then dichloromethane and water were used for extractionAfter distillation under reduced pressure, the residue was subjected to silica gel column, and the solvent was distilled off under reduced pressure to obtain Compound A1 (5.35 g, 12.23 mmol). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50 mmol | Step1. Dissolve 100 mmol of <strong>[1190360-23-6]3-bromo-9,9-dimethylfluorene</strong> in anhydrous THF and cool to - 78 C, argon.Under the protection of gas, 1.5 equivalents of n-butyllithium was added and reacted for 1 h. The temperature was slowly raised to room temperature, triphenylgermanium chloridewas added, and the reaction was completed in 1 h. The reaction was quenched with EtOAc EtOAc.The silica gel column was passed to give the product 37 50 mmol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; for 2h;Reflux; | Tri-tert-butylphosphine (4.4 mL of a 1.0 M solution in toluene, 1.48 g, 0.05 mmol),Palladium acetate (0.4 g, 1.83 mmol) and sodium tert-butoxide (22.8 g, 238 mmol)Addition to N,N'-diphenylbenzidine (61.5 g, 183 mmol)And 3-bromo-9,9-dimethyl-fluorene (49.9g, 183mmol) (1L) was degassed in toluene,And the mixture was heated under reflux for 2 hours. The reaction mixture was cooled to room temperature.Dilute with toluene and filter through celite. The filtrate was diluted with water and extracted with toluene.The organic phases were combined and evaporated under vacuum.The residue was filtered through silica gel and recrystallized.Intermediate a1-6 (77.3 g, yield 80%) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 12h;Reflux; Inert atmosphere; | 13.66 g (50 mmol) of compound A-1,11.60 g (60 mmol) of compound B-1,17.30 g (180 mmol) of sodium tert-butoxide and 0.31 g (1.5 mmol)Tri-tert-butylphosphine is dissolved in 400 ml of toluene.Then 0.86 g (1.5 mmol) of tris(dibenzylideneacetone)dipalladium was added.The reaction was refluxed for 12 hours under a nitrogen atmosphere. After the reaction,It was extracted with toluene and distilled water, and the organic phase was dried over anhydrous magnesium sulfate.Filtration, and then removing the organic solvent by distillation under reduced pressure.Finally purified by silica gel column chromatography using n-hexane/dichloromethane system.And recrystallized in a mixed solution of dichloromethane/n-hexane.You can get 15.42g(40 mmol) of intermediate C-1,The yield was 80%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67.5% | 1 g of <strong>[1190360-23-6]3-bromo-9,9-dimethylfluorene</strong> (3.6 mmol) under nitrogen And 80 mL of anhydrous tetrahydrofuran was added to a 250 mL dry two-neck round bottom flask.Stir and cool to -78 C.A solution of 1.8 mL of material in a concentration of 2 M n-butyllithium tetrahydrofuran (4.3 mmol)Add dropwise to the reaction system, after 1 h of reaction,2.0 g of isopropanol pinacol borate (10.8 mmol) was added to the reaction system.Slowly return to room temperature and stir overnight. Quench the reaction by adding 5 mL of water.Add 80 mL of dichloromethane and extract twice.The organic layer was concentrated. After the crude product obtained is purified by column chromatography,0.79 g of a white solid were obtained in a yield: 67.5%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With potassium phosphate; copper(l) iodide; trans-1,2-cyclohexanediamine; In toluene; at 110℃; for 12h;Inert atmosphere; | Under the environment of nitrogen, will (9.2 g, 20 mmol) compound 1 - 44 - 2, (5.46 g, 20 mmol) compound 1 - 44 - 3, (1.91 g, 10 mmol) cuprous iodide, (2.28 g, 20 mmol) anti-form link oneself diamine, (12.72 g, 40 mmol) potassium phosphate and 100 ml toluene is added to 300 ml bottle in three, heating and stirring to 110 C reaction 12 hours, the end of the reaction, cooling to room temperature, filtered and the filtrate, rotary evaporated most of the solvent, dichloromethane is used for dissolving water washing 3 times, to collect organic the fluid mixes purified by silica gel column, to obtain compound 1 - 44, yield 66%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.47 g | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 60℃; for 5h; | In a 100 ml round-bottom flask, 0.5 g (2.56 mmol) of Compound M1, 0.82 g (3.0 mmol) of <strong>[1190360-23-6]3-bromo-9,9-dimethyl-9H-fluorene</strong>, 1.14 g (5.6 mmol) of sodium tert-butoxide, 0.09 g (0.1 mmol) of tris(dibenzylideneacetone)dipalladium (0), and 14.8 mg (0.15 mmol) of tri-tert-butylphosphine were dissolved in 30 ml of toluene, and then the resulting solution was stirred in a bath at 60 C. for 5 hours. When the reaction was completed, toluene was removed, followed by column separation using dichloromethane and n-hexane, thereby obtaining 0.47 g (1.2 mmol) of Compound M3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; In toluene; at 105℃; for 24h;Inert atmosphere; | In a 250ml three-necked bottle, under nitrogen protection,Add 0.01 mol of raw material L1, 0.012 mol of raw material O1, 150 mlMixing toluene,Then, 6×10-5 mol of Pd2(dba)3, 6×10-5 mol of triphenylphosphine, 0.03 mol of sodium t-butoxide, and heating to 105 C. were added, and the reaction was refluxed for 24 hours.Sampling point plate, showing no bromine residue remaining, the reaction is complete; naturally cooled to room temperature, filtered, the filtrate is rotary evaporated to no fraction, passed through a neutral silica gel column to obtain Bn intermediate I-1; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78.4% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 90℃; for 10h;Inert atmosphere; | Intermediate E-1 was prepared according to the method in Example 1. Intermediate E-1 (0.1 mmol) and intermediate F-16 (0.1 mmol) were added to dry toluene, and sodium tert-butoxide (0.2 mmol) and tri-tert-butyl were added under the protection of nitrogen under nitrogen. The phosphine (0.02 mmol) was tris(dibenzylideneacetone)dipalladium (0.001 mmol); the mixed solution of the above reactants was reacted at a reaction temperature of 90 C for 10 hours under a nitrogen atmosphere, and the reaction solution was cooled and filtered. The filtrate was rotary-screwed and passed through a silica gel column (PE: DCM = 10:1) to afford product compound 16 (yield: 78.4%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 100℃; for 12h;Inert atmosphere; | Intermediate E'-54 (13.0 g, 36.2 mmol) and intermediate F'-54 (9.85 g, 36.2 mmol) were completely dissolved in 200 mL of dry toluene in a 500 mL round bottom flask under a nitrogen atmosphere. Sodium tert-butoxide (6.95 g, 72.4 mmol) was added followed by tri-tert-butylphosphine (1.46 g, 7.24 mmol) and tris(dibenzylideneacetone)dipalladium (0.33 g,0.36 mmol), the resultant was heated to 100 C and stirred for 12 hours. After the temperature was lowered to room temperature, the resultant was filtered to remove the salt, the toluene was concentrated, and the obtained product was subjected to column chromatography using dichloromethane: petroleum ether = 1:5 to give compound 54 (16.76 g, yield: 84%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 90℃; for 10h;Inert atmosphere; | Intermediate E-1 was prepared according to the method in Example 1. Intermediate E-1 (50 mmol) and intermediate F-16 (50 mmol) were added to dry toluene (500 mL). Sodium tert-butoxide (100 mmol) and tri-tert-butylphosphine (10 mmol) were added to tris(dibenzylideneacetone)dipalladium (0.5 mmol) under a nitrogen atmosphere; the mixed solution of the above reactants was placed under a nitrogen atmosphere. The reaction was carried out at a reaction temperature of 90 C for 10 hours, and the reaction solution was cooled and filtered, and the filtrate was evaporated to dryness to silica gel column (PE:DCM=10:1) to give product compound 16 (38.5 mmol). The yield was 77%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73.2% | With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; XPhos; In 5,5-dimethyl-1,3-cyclohexadiene; for 24h;Inert atmosphere; Reflux; | 9.9-Dimethyl-3-bromoindole was sequentially introduced into a dry 5L four-necked flask.273.2 g (1.0 mol, 99%, 1.0 eq.),O-chloroaniline 153.1 g (1.2 mol, 99%, 1.2 eq.),Pd2dba3 catalyst 5.49g (0.006mol, 97%, 0.6% eq.),X-phos ligand 5.72 g (0.012 mol, 99%, 1.2% eq.),Sodium tert-butoxide 192.2 g (2 mol, 98%, 2.0 eq.) and xylene 2.8 kg,Replaced with nitrogen three times and heated under reflux with nitrogen for 24 h, TLC detection,The reaction starting material 9,9-dimethyl-3-bromoindole was completely converted.After the reaction was completed, the temperature was lowered to room temperature, and quenched by adding 500 g of ice water, stirred for 1 hour, and layered.The organic phase is retained; the organic phase is washed twice with 2*250 g of water; the organic phase is concentrated to recover the solvent xylene; a brown-red viscous liquid is obtained, which is recrystallized from dichloromethane and n-hexane.207.4 g of a pale yellow solid was obtained in a yield of 73.2%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 3h;Inert atmosphere; Heating; | Compound E (19.80g, 31.29mmol), in 500ml round bottom flask in nitrogen atmosphere <strong>[1190360-23-6]3-bromo-9,9-dimethyl-9H-fluorene</strong> (8.54 g, 31.29 mmol)After completely dissolved in 300 ml of tetrahydrofuran,2M aqueous potassium carbonate solution (150 ml) was added,After adding tetrakis- (triphenylphosphine) palladium (1.08g, 0.93mol),Heat stirring for 3 hours.Lower the temperature to room temperature (23 ± 5 ), remove the water layer, After drying over anhydrous magnesium sulfate and concentrated under reduced pressure,Compound 5 (12.5 g, 52%) was prepared by recrystallization with 180 ml of ethyl acetate. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene;Reflux; | In a round bottom flask, 20.0 g of the above <strong>[1190360-23-6]3-bromo-9,9-dimethyl-9H-fluorene</strong> (<strong>[1190360-23-6]3-bromo-9,9-dimethyl-9H-fluorene</strong>) and 16.9 g of 9,9-dimethyl-9H-fluoren-2-amine, 10.5 g of t-BuONa, 2.7 g of Pd2 (dba) 3, and 3.3 ml of (t-Bu) 3P were dissolved in 400 ml of toluene, and then stirred under reflux.The reaction was confirmed by thin-layer chromatography, and after adding water, the reaction was completed.The organic layer was extracted with methyl cellulose, filtered under reduced pressure, and then recrystallized to obtain 18.5 g (yield 63%) of OP1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; sodium t-butanolate; In toluene; at 90℃; for 5h;Inert atmosphere; | In a 1000 mL single-necked flask, add 13.5 g (50 mmol) of 2-amino-4-methoxy-5'-methoxy-1,2'-biNaphthalene, 13.5 g (50 mmol) of 2-bromo-9,9'-dimethylfluorene, 0.7 g (1 mmol) of [1,1, -bis (diphenylphosphine) ferrocene] dichloridePalladium, 0.5 g of 2-dicyclohexylphosphine-2 ', 6'-dimethoxybiphenyl, 500 mL of toluene, 14.4 g (150 mmol) of sodium tert-butoxide, extractedNitrogen was replaced 3 times, and the reaction was heated to 90C for 5h. When the reaction is complete, stop the reaction. Cool to room temperature, separate the reaction solution and concentrateThe organic phase was shrunk, methanol was added and stirred for 1 h, and suction filtration was performed to obtain a light yellow powder M2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; In toluene; at 110℃; for 5h;Inert atmosphere; | In a 1000 mL single-necked flask, 13.5 g (50 mmol) of 2-amino-1,1'-binaphthalene, 27 g (100 mmol) of <strong>[1190360-23-6]3-bromo-9,9'-dimethylfluorene</strong>, and 0.9 g (1 mmol) of tris (2) Benzylideneacetone) dipalladium, 0.5g of 2-dicyclohexylphosphine-2 ', 6'-dimethoxybiphenyl, 500mL of toluene, 14.4g (150mmol) of sodium tert-butoxide, evacuation and nitrogen for 3 times, reaction The temperature was raised to 110 C for 5h. When the reaction is complete, stop the reaction. Cool to room temperature, separate the reaction solution, concentrate the organic phase, add methanol and stir for 1 h, and suction filter to obtain a light yellow powder P170 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; sodium t-butanolate; In toluene; at 90℃; for 5h;Inert atmosphere; | In a 1000 mL single-necked flask, 23 g (50 mmol) of M1, 13.5 g (100 mmol) of <strong>[1190360-23-6]3-bromo-9,9'-dimethylfluorene</strong>, 0.9 g (1 mmol) of tris (dibenzylideneacetone) dipalladium, and 500 mL of toluene were added. , Vacuum was used to change the nitrogen for 3 times, and 0.5 mL of tri-tert-butylphosphine toluene solution was added, and the temperature was raised to 110 C for 12 hours. After the reaction was completed, the solvent was distilled off and silica gel column chromatography was performed to obtain P387. | |
With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; 1,3-bis[(2,6-diisopropyl)phenyl]imidazolinium chloride; In toluene; at 90℃; for 5h;Inert atmosphere; | In a 1000mL single-necked bottle, add 13.5g (50mmol) M1, 13.6g (50mmol) 3-bromo-9, 9-dimethylfluorene, 0.9g (1mmol) tris (dibenzylideneacetone) dipalladium (ie Pd2 (dba) 3), 0.5g IPr.HCl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide (NaOBu-t), evacuated for 3 times with nitrogen, the reaction was heated to 90 C for 5h. When the reaction is complete, stop the reaction. After cooling to room temperature, the reaction solution was separated, the organic phase was concentrated, methanol was added and stirred for 1 h, and suction filtration was performed to obtain light yellow powder M1-1. |
Tags: 1190360-23-6 synthesis path| 1190360-23-6 SDS| 1190360-23-6 COA| 1190360-23-6 purity| 1190360-23-6 application| 1190360-23-6 NMR| 1190360-23-6 COA| 1190360-23-6 structure
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P273 | Avoid release to the environment. |
P280 | Wear protective gloves/protective clothing/eye protection/face protection. |
P281 | Use personal protective equipment as required. |
P282 | Wear cold insulating gloves/face shield/eye protection. |
P283 | Wear fire/flame resistant/retardant clothing. |
P284 | Wear respiratory protection. |
P285 | In case of inadequate ventilation wear respiratory protection. |
P231 + P232 | Handle under inert gas. Protect from moisture. |
P235 + P410 | Keep cool. Protect from sunlight. |
Response | |
Code | Phrase |
P301 | IF SWALLOWED: |
P304 | IF INHALED: |
P305 | IF IN EYES: |
P306 | IF ON CLOTHING: |
P307 | IF exposed: |
P308 | IF exposed or concerned: |
P309 | IF exposed or if you feel unwell: |
P310 | Immediately call a POISON CENTER or doctor/physician. |
P311 | Call a POISON CENTER or doctor/physician. |
P312 | Call a POISON CENTER or doctor/physician if you feel unwell. |
P313 | Get medical advice/attention. |
P314 | Get medical advice/attention if you feel unwell. |
P315 | Get immediate medical advice/attention. |
P320 | |
P302 + P352 | IF ON SKIN: wash with plenty of soap and water. |
P321 | |
P322 | |
P330 | Rinse mouth. |
P331 | Do NOT induce vomiting. |
P332 | IF SKIN irritation occurs: |
P333 | If skin irritation or rash occurs: |
P334 | Immerse in cool water/wrap n wet bandages. |
P335 | Brush off loose particles from skin. |
P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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