Structure of 7427-09-0
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The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
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CAS No. : | 7427-09-0 |
Formula : | C11H9NO2 |
M.W : | 187.19 |
SMILES Code : | O=C1C(C)=C(N)C(C2=CC=CC=C21)=O |
MDL No. : | MFCD00667088 |
InChI Key : | MRYHMFJDZYADEB-UHFFFAOYSA-N |
Pubchem ID : | 12251093 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H335 |
Precautionary Statements: | P261-P280-P301+P312-P302+P352-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 |
---|---|---|
69% | With hydrogenchloride; sodium azide; In methanol; at 50℃; for 5.0h;pH 4.0;Inert atmosphere; | 2-amino-3-methyl-l,4-naphthoquinone (le). Dissolved 2-methyl-l,4-naphthoquinone (560 mg, 3.3 mmol) in methanol (30 mL) and placed under inert atmosphere. Dissolved 1.37 g NaN3 in 10 mL water and acidified to pH 4 (83 drops of 12 M HC1). Added sodium azide solution to reaction flask and slowly heated reaction to 50C and then stirred for 5 hrs. Reaction was quenched with water and extracted with ethyl acetate (2x) The organic layers were combined and washed with saturated NaCl solution, dried with Mg2S04, and concentrated in vacuo. The reaction was purified on silica gel eluting with ethyl acetate and hexane (3 :7) to yield 423 mg orange powder le (69% yield). MS m/z calcd (M+) 188.07, found 188.04. 1H NMR (400 MHz, DMSO-d6) Shift 7.96 - 8.03 (m, 2H), 7.83 (dt, J = 1.25, 7.53 Hz, 1H), 7.71 - 7.78 (m, 1H), 6.86 (s, 2H), 1.97 (s, 3H). C13-HSQC (400 MHz, DMSO-d6) Shift 0.53, 28.28, 9.45, 39.58, 132.22, 125.73, 134.80, 125.94, 125.93, 134.81. |
35% | With trimethylsilylazide; at 20℃; for 216.0h; | So a suspension of 2- methylnaphthalene- 1 ,4-dione (173 mg, l.O mmol) was added azidotrimethylsilane (134 1.0 mmol) and the mixture was stirred at room temperature for 9 days, after which time 0.2 M aq. citric acid (10 mL) was added and stirred 30 min. The insoluble material was collected via vacuum filtration and the solids washed with water and dried in vacuo and purified via MPLC (silica, 0-6% MeOH/CH2Cl2). Yield: 66 mg, 35%. lR NMR (400 MHz, DMSO-i δ 7.93 (dd, J = 7.6, 1.4 Hz, 2H), 7.77 (td, J= 7.6, 1.3 Hz, 1H), 7.68 (td, J= 7.5, 1.4 Hz, 1H), 6.78 (s, 2H), 1.92(s, 3H); C NMR (126 MHz, DMSO) δ 181.30, 146.91, 134.39, 132.97, 132.03, 130.20, 125.39, 110.38, 9.62; HRMS (ESI-TOF) m/z: [M + H]+ Calcd for CnH10NO2 188.0706; Found 188.0695 |
With hydrogenchloride; sodium azide; In ethanol; water; for 36.0h;pH 4.0;Reflux; | General procedure: To a previously stirred solution of 2 g of 1 in 100 mL of ethanol was added 4.74 g of sodiumazide in 34 mL of distilled water, then adjusted to pH 4 with HCl and allowed to stir for 15 h at refluxtemperature. After completion of the reaction time, extraction was performed with ethyl acetate (3 x 100 mL). The organic extracts were washed with saline solution, dried over anhydrous Na2SO4 andconcentrated. The residue was crystallized from a mixture of diethyl ether/hexane to afford an orangepowder; 90% yield |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With hydrogen bromide; acetic acid; at 20℃; | General procedure: 2-Amino-1,4-naphthoquinone 3a (100 mg, 0.56 mmol) was dissolved in acetic acid (2 mL), after which a 33% solution of HBr in acetic acid (0.1 mL) and the aldehyde (2.8 mmol) were added dropwise. It is important to prevent evaporation of the aldehyde by means of a reflux condenser. The reaction mixture was stirred at room temperature from 24 h to 48 h and followed to completion by TLC (Petroleum ether/EtOAc, 2/1). After completion the reaction mixture was diluted with water and extracted with diethyl ether. The combined organic extracts were washed with aqueous sodium bicarbonate, aqueous sodium sulphite and brine. Drying over MgSO4, followed by filtration and concentration in vacuo gave the corresponding product in moderate to good yield and more than 95% purity (HPLC). Eventually recrystallisation may be performed in Et2O/heptane |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30% | at 150℃; for 0.333333h;Microwave irradiation; | General procedure: A 10 mL microwave tube was loaded with 6a or 6b (1.4 mmol), paraformaldehyde (4 mmol), the appropriate thiol (1.5 mmol) and chloroform (5 mL) and were irradiated for 20 min. The internal temperature reached 150 C. The solvent was evaporated under reduced pressure. The residual solid product was purified by column chromatography on silica gel and eluted with an increasing polarity gradient mixture of hexane and ethyl acetate (9/1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With palladium 10% on activated carbon; hydrogen; In ethyl acetate; at 25 - 30℃; for 6.0h; | For the preparation of amino derivative (NH2-VK3), to a stirred solution of the nitro derivative (1.0 eqv.) in ethyl acetate (10 mL), 10% Pd on carbon (10% load) was added. The reaction was carried out at 5 kg of hydrogen pressure for 6 h at 25-30 C. The progress of the reaction was monitored by TLC. After completion of the reaction, the reaction mixture was filtered through celite bed, washed with ethyl acetate and concentrated to afford the amine compounds as brownish red solid (Yield: 90%). |