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CAS No. : | 1204-79-1 | MDL No. : | MFCD00463439 |
Formula : | C12H11NO | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | LQZZZAFQKXTFKH-UHFFFAOYSA-N |
M.W : | 185.22 g/mol | Pubchem ID : | 14565 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P264-P270-P271-P280-P301+P312-P302+P352-P304+P340-P305+P351+P338-P330-P332+P313-P337+P313-P362-P403+P233-P405-P501 | UN#: | |
Hazard Statements: | H302-H312-H315-H319-H332-H335 | Packing Group: | |
GHS Pictogram: |
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* 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 |
---|---|---|
41.1% | With N-ethyl-N,N-diisopropylamine; In N,N-dimethyl-formamide; at 0 - 23℃; for 16h;Inert atmosphere; | Di-tert-butyl dicarbonate (0.860 g, 3.94 mmol) was added to 4'-amino-[l,l'-biphenyl]-4-ol (0.73 g, 3.94 mmol), DIEA (2.065 mL, 11.82 mmol) in DMF (10 mL) at 0Cunder nitrogen. The resulting mixture was stirred at rt for 16 h. The reaction mixture was concentrated and diluted with DCM (50 mL) then washed sequentially with water (3 x 50 mL) and saturated brine (50 mL). The organic layer was dried over Na2S0 , filtered and evaporated to afford crude product. The crude product was purified by flash silica chromatography, elution gradient 0 to 20% MeOH in DCM. Pure fractions were evaporated to dryness to afford tert-butyl (4'-hydroxy-[l,l'-biphenyl]-4- yl)carbamate (0.462 g, 41.1 %) as a yellow solid. NMR (300 MHz, DMSO) d 1.46 (s, 9H), 6.74 - 6.83 (m, 2H), 7.36 - 7.51 (m, 6H), 9.35 (s, 1H), 9.44 (s, 1H). ES+m/z [M-tBu]+: 230, HPLC tR= 1.33 min (97.0%). |
In DMF (N,N-dimethyl-formamide); at 20℃; | [0167] Example 15: Synthesis OF 4 -(2-METHOXY-2-OXOETHOXY)-1, 1 -BIPHENYL-4- aminium chloride. [0168] Step 1: (4 -HYDROXY-BIPHENYL-4-YL)-CARBAMIC acid ter-butyl ester. Triethylamine (786 PAL, 5.64 mmol) and DI-TE7T-BUTYL dicarbonate were added to a solution of 4'- amino-biphenyl-4-ol (0.5 g, 1.88 mmol), prepared in step 4 of Example 13, in DMF. After the addition the reaction stirred at room temperature overnight. The solvent was removed under reduced pressure and the residue partitioned between water and ethyl acetate. The aqueous layer was separated and extracted multiple times with ethyl acetate. The combined extracts were washed with brine, dried (NA2S04) and the solvent removed under reduced pressure to give (4'- hydroxy-biphenyl-4-yl) -carbamic acid tert-butyl ester. The material was used in subsequent reactions without purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium chloride; In tetrahydrofuran; chloroform; N,N-dimethyl acetamide; | Example 96 43 mg of 4'-aminobiphenyl-4-ol was dissolved in 0.7 ml of N,N-dimethylacetamide, and 107 mg of sulfamoyl chloride was added thereto under cooling with ice, followed by stirring at room temperature for 2.4 hours. After the reaction mixture was poured into a saturated aqueous solution of sodium chloride, the product was extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous magnesium sulfate. After the solvent was distilled off, the resulting crude product was purified by TLC (using a 17:10 mixture of chloroform and tetrahydrofuran as the developing solvent) to obtain 42 mg of 4'-(sulfamoylamino)biphenyl-4-yl sulfamate. 1H-NMR(CD3OD, δ): 7.30(2H, d, J=8.7Hz), 7.37(2H, d, J=8.7Hz), 7.56(2H, d, J=8.7Hz), 7.63(2H, d, J=8.7Hz). MS(m/z): 343(M+), 264, 184. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
11%; 78% | In dichloromethane; at 20℃; for 0.0833333h; | General procedure: 7-Bromo-2-methylquinoline-5,8-dione (5) or 7-bromoquinoline-5,8-dione (6) (19.92 mmol, 1 equiv) was dissolved in dichloromethane (30 mL) and amine (59.78, 3 equiv) was added. After stirring for 5 min at rt, H2O (50 mL) was added into the mixture and extracted with dichloromethane, dried by Na2SO4 and concentrated in vacuo. The residue was puried by ash column chromatography (EtOAc/n-hexane 40:60 to 50:50) to give 7a-e, 8a-e, 9a-e, and 10a-e. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
11%; 76% | In dichloromethane; at 20℃; for 0.0833333h; | General procedure: 7-Bromo-2-methylquinoline-5,8-dione (5) or 7-bromoquinoline-5,8-dione (6) (19.92 mmol, 1 equiv) was dissolved in dichloromethane (30 mL) and amine (59.78, 3 equiv) was added. After stirring for 5 min at rt, H2O (50 mL) was added into the mixture and extracted with dichloromethane, dried by Na2SO4 and concentrated in vacuo. The residue was puried by ash column chromatography (EtOAc/n-hexane 40:60 to 50:50) to give 7a-e, 8a-e, 9a-e, and 10a-e. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | In ethanol; dichloromethane; for 1h;Reflux; | General procedure: A solution of 2-hydroxynapthoquinone (12) (1 equiv) in 5 mL of dichloromethane was added dropwise to a solution of appropriate amine (3 equiv) in 15 mL of EtOH. The reaction was refluxed for 1 h. After concentration in vacuo, the residue was directly puried by ash column chromatography (EtOAc/n-hexane 40:60 to 50:50) to give 13-15. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With pyridine; In dichloromethane; for 12h; | N-(4'-hydroxy-[1,1'-biphenyl]-4-yl)-3',6-dimethoxy-[1,1'-biphenyl]-3-carboxamide (54) A solution of acid chloride (5b, 0.27 mmol), in anhydrous dichloromethane (2 mL) was added to a solution of the aniline (53, 0.18 mmol) and anhydrous pyridine (0.94 mmol) in anhydrous dichloromethane (5 mL). After 12 h, the solvent was removed and the residue purified via column chromatography (SiO2, 10:1, DCM: methanol) to afford 54 as a off-white amorphous solid (62%). 1H NMR (500 MHz, DMSO-d6) δ 9.50 (s, 1H, NH), 8.02 (dd, J = 8.6, 2.4 Hz, 1H), 7.98 (d, J = 2.4 Hz, 1H), 7.82 (d, J = 8.7 Hz, 2H), 7.56 (d, J = 8.7 Hz, 2H), 7.49 (d, J = 8.6 Hz, 2H), 7.37 (t, J = 7.9 Hz, 1H), 7.25 (d, J = 8.7 Hz, 1H), 7.15- 7.07 (m, 2H), 6.95 (ddd, J = 8.3, 2.6, 1.0 Hz, 1H), 6.84 (d, J = 8.6 Hz, 2H), 3.86 (s, 3H), 3.80 (s, 3H). 13C NMR (126 MHz, DMSO) δ 164.61, 158.93, 158.66, 156.75, 138.82, 137.79, 135.24, 130.51, 129.79, 129.19, 129.11, 129.06, 127.29, 126.91, 125.89, 121.74, 120.63, 115.64, 115.16, 112.53, 111.39, 55.83, 55.07. HRMS (ESI+) m/z [M+Na+] calcd for C27H23NO4Na 448.1525; found 448.1522. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
General procedure: Under an atmosphere of N2, 0.175 g (1 mmol) compd. 2 was dissolved in methanol, 0.11 mL (1.05 mmol) salicylaldehyde was added and stirred overnight at room temperature. When compd. 2 disappeared, NaBH4 (61 mg, 1.6 mmol) was added. After stirring for 10 min, the reaction was quenched by sat. NH4Cl solution, then extracted with CH2Cl2 (3×20 mL), and the organic layer was washed with saturated NaCl aqueous solution, dried over anhydrous Na2SO4 and purified by flash chromatography (PE:EtOAc = 15:1) to afford 0.230 g (82%) E6 as white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate; In 1,4-dioxane; water;Inert atmosphere; Reflux; | General procedure: To 0.329 g (1.5 mmol) 4-iodoaniline, 1.8 mmol ArB(OH)2, 0.318 g (3 mmol) Na2CO3 and 75 mg (0.075 mmol) PdCl2(PPh3)2, 15 mL of a blended solution of dioxane and water (v/v = 3/1) was added under N2 atmosphere. Then the reaction was heated to reflux and monitored by TLC. Upon cooling, the reaction mixture was dilute with sat. NH4Cl solution, then extracted with EA (3×20 mL), and the organic layer was washed with saturated NaCl aqueous solution, dried over anhydrous Na2SO4 and purified by flash chromatography to afford different 4-aminobiphenyl derivatives. According to the reductive amination procedure, the 4-aminobiphenyl derivative was further treated with salicylaldehyde and to afford the corresponding compound 5&6. |
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