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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.
2-Benzoxazolinone (BOA), a well-known allelochemical with strong phytotoxicity, is a potential herbicidal candidate and probably functions via interfering with auxins or disrupting membrane integrity.
Synonyms: 2-Benzoxazolone; 1,3-Benzoxazol-2(3H)-one; 2-Hydroxybenzoxazole
4.5
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CAS No. : | 59-49-4 |
Formula : | C7H5NO2 |
M.W : | 135.12 |
SMILES Code : | O=C1OC2=CC=CC=C2N1 |
Synonyms : |
2-Benzoxazolone; 1,3-Benzoxazol-2(3H)-one; 2-Hydroxybenzoxazole
|
MDL No. : | MFCD00005716 |
InChI Key : | ASSKVPFEZFQQNQ-UHFFFAOYSA-N |
Pubchem ID : | 6043 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302+H312+H332 |
Precautionary Statements: | P280 |
* 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 |
---|---|---|
94% | With bromine; acetic acid; at 20℃; for 4h; | 3H-1,3-Benzoxazol-2-one (5.00 g, 37.00 mmol) was dissolved in acetic acid (50 mL) and bromine (1.9 mL, 37.0 mmol) was added dropwise. The reaction mixture was stirred at 20 C for 4 h.The reaction mixture was poured onto ice and the precipitate was collected by filtration, washed with water and air-dried to give a pink powder (7.48 g, 34.8 mmol, 94%). Mp 191.6-192.3 C. 1H NMR (300 MHz, DMSOd6): δ 11.81 (s, 1H), 7.57 (dd, J = 1.9 Hz, J = 0.3 Hz, 1H), 7.30 (dd, J = 8.3 Hz, J = 1.9 Hz, 1H), 7.04 (dd, J = 8.3 Hz, J = 0.3 Hz, 1H). 13C NMR (75 MHz, DMSOd6): δ 154.5, 144.5, 130.3, 126.9, 113.5, 113.2, 111.7. LCMS m/z calc for [M - H]+: 211.9, 213.9, found: 211.8, 213.8. |
94% | 3H-1,3-Benzoxazol-2-one (5.00 g, 37.00 mmol) was dissolved in acetic acid (50 mL) and bromine (1.9 mL, 37.0 mmol) was added dropwise. The reaction mixture was stirred at20C for 4 h. The reaction mixture was poured onto ice and the precipitate was collected by filtration, washed with water and air-dried to give 1 as a pink powder (7.48 g, 94%). Mp 191.6C. 1H NMR (300 MHz), (5(ppm, DMSO-d6): 11.81 (s, 1H), 7.57 (dd, J= 1.9 Hz, J0.3 Hz, 1H), 7.30 (dd, J= 8.3 Hz, J= 1.9 Hz, 1H), 7.04 (dd, J 8.3 Hz, J 0.3 Hz, 1H).13C NMR (75 MHz), (5(ppm, DMSO-d6): 154.5, 144.5, 130.3, 126.9, 113.5, 113.2, 111.7.LCMS m/zcalc for [M-H]: 211.9, 213.9, found: 211.8, 213.8. | |
84% | With bromine; In dichloromethane; at 20℃; for 19.5h; | To a mixture of 3H-benzooxazol-2-one (20 g, 0.15 mol) in DCM (500 mL) was added bromine (8.34 mL, 0.16 mol). After stirring at room temperature for 19.5 h, the orange precipitate that had formed was filtered off and washed with DCM until the orange color was washed out. The filtrate was concentrated to approximately 33% of its original volume and filtered and washed as before. The combined solids weighed 28.36 g. 1H NMR indicated the product was clean albeit contained ca. 8-9% starting material meaning the true yield of product was 26.72 g, 84%. |
70% | With N-Bromosuccinimide; In acetic acid; at 20℃; for 72h; | Step 1: N-Bromosuccinimide (26.6 g, 0.15 mol) was added to a stirred solution of 2-benzoxazolinone (20.0 g, 0.15 mol) in glacial acetic acid (220 mL), and the mixture was stirred at room temperature for 3 days. The reaction mixture was poured into H2O (1.2 L), and the white solid that formed was collected. Recrystallization from hot EtOH (300 mL) gave bromide 1 (22.1 g, 70%) as an off-white solid: mp 190-195 C.; IR (KBr): 3278, 1779, 1736, 1623 cm?1; 1H NMR (300 MHz, CD3OD): ?7.41 (d, J=2 Hz, 1H), 7.32 (dd, J=5, 2 Hz, 1H), 6.99 (d, J=5 Hz, 1H); CI MS (methane) (m/z): 215 [M+H]+. |
31% | With N-Bromosuccinimide; In acetonitrile; at -15 - 20℃; | Preparation of 6-Bromo-3H-benzoxazol-2-one. To a stirred suspension of 3H-benzoxazol-2-one (1.35 g, 10 mmol) in acetonitrile (23 ML) at -15 C. was added portionwise NBS (2.00 g, 11.0 mmol).Following complete addition of NBS the mixture was stirred at -15 to 0 C. for 3 h then allowed to warm to ambient temperature and stirred overnight.The solvent was evaporated in vacuo and the residue was partitioned between CH2Cl2/H2O precipitating the intermediate title compound, 6-bromo-3H-benzoxazol-2-one, (0.67 g, 31%) as a brown solid. 1HNMR(CDCl3) δ 7.0 (1H, d), 7.15 (1H.,d), 7.3 (1H, s), 11.9 (1H, s). |
With bromine; In dichloromethane; at 20℃; for 19.5h; | To a mixture of 3H-benzooxazol-2-one (20 g, 0.15 mol) in DCM (500 mL) was added bromine (8.34 mL, 0.16 mol). After stirring at room temperature for 19.5 h, the orange precipitate that had formed was filtered off and washed with DCM until the orange color was washed out. The filtrate was concentrated to approximately 33% of its original volume and filtered and washed as before. The combined solids weighed 28.36 g and contained ca. 8-9% starting material. | |
With N-Bromosuccinimide; In water; acetic acid; | Step 1: To a solution of benzoxazolinone (20 g, 0.148 mol) in 220 mL glacial acetic acid was added N-bromosuccinimide (NBS, 26.36 g, 0.148 mol), and the reaction mixture was stirred at room temperature for 63 hours before pouring into 1500 mL water. The precipitated product was washed thoroughly with water upon collection and recrystallized from EtOH to give 6-bromo-3H-benzoxazol-2-one (9) (25.09 g, 79%): Theory: C, 39.28; H, 1.88; N, 6.54; Br, 37.33. Found: C, 39.36; H, 2.02; N, 6.36; Br, 37.43. MP 192-194 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In tetrahydrofuran; | (i) 1,1-Dimethylethyl 4-(2-oxo-1,3-benzoxazol-3(2H)-yl)piperidine-1-carboxylate 2-Benzoxazolinone (1 g) was added to a cooled solution of triphenylphoshine (2.13 g) and diethylazodicarboxylate (1.28 ml) in dry tetrahydrofuran (20 ml). After 10 min at 0 C., N-(t-butoxy)-4-hydroxypiperidine (1.63 g) (Tetrahedron Letters, 1996, 6439-6442) was added portionwise. The reaction mixture was stirred at room temperature for 16 h. The solution was diluted with water, extracted with ethyl acetate, dried and evaporated under reduced pressure. Purification was by chromatography eluding with (1:2) diethylether/isohexane. Yield 0.5 g as an oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With trifluorormethanesulfonic acid; In dichloromethane; ethyl acetate; | EXAMPLE 251A 6-bromo-1,3-benzoxazol-2(3H)-one A mixture of 2-benzoxazolinone (3.00 g, 22.2 mmol), 1,3-dibromo-5,5-dimethylhydantoin (3.49 g, 12.2 mmol), and trifluoromethanesulfonic acid (5.00 g, 33.3 mmol) in dichloromethane (100 mL) at room temperature was protected from light, stirred for 1 hour, and concentrated. The concentrate was purified by flash column chromatography on silica gel with 50% ethyl acetate/hexanes to provide the desired product. | |
With trifluorormethanesulfonic acid; In dichloromethane; ethyl acetate; | Example 251A 6-bromo-1,3-benzoxazol-2(3H)-one A mixture of 2-benzoxazolinone (3.00 g, 22.2 mmol), 1,3-dibromo-5,5-dimethylhydantoin (3.49 g, 12.2 mmol), and trifluoromethanesulfonic acid (5.00 g, 33.3 mmol) in dichloromethane (100 mL) at room temperature was protected from light, stirred for 1 hour, and concentrated. The concentrate was purified by flash column chromatography on silica gel with 50% ethyl acetate/hexanes to provide the desired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With triethylamine; In tetrahydrofuran; at 70℃; for 6h; | General procedure: To a solution of 4a or 4b (1mol equiv.) in anhydrous THF was added TEA (3mol equiv.). The mixture was added drop wise the solution of acyl chlorides (1.1mol equiv.) in anhydrous THF at 0C and stirred at 70C for 6h. The water was added to quench the reaction. The mitxure was extracted with ethyl acetate to afford the crude product that was purified by flash column chromatography on silica gel to yield the target products.4.1.6.1 3-(2-(4-Fluorophenyl)acetyl)benzo[d]oxazol-2(3H)-one (9a) (0050) White solid. Yield 86%. Mp 180-182C. 1H NMR (300MHz, DMSO-d6): δ(ppm) 7.98-7.89 (m, 1H), 7.50-7.41 (m, 1H), 7.41-7.28 (m, 4H), 7.24-7.14 (m, 2H), 4.41 (s, 2H). MS (EI): m/z 272.2 [M+H]+. IR (KBr): 3067, 1796, 1721, 1601, 1514, 1248cm-1. |
86% | With triethylamine; In tetrahydrofuran; water; at 70℃; for 6h;Cooling with ice; | A solution of 1a (0.10 g, 0.74 mmol) was dissolved in 10 mL of dry tetrahydrofuran,Triethylamine (0.22 g, 2.22 mmol) was added to the acid,No addition of p-fluorophenyl acetyl chloride to the ice bathWater tetrahydrofuran solution (0.15 g, 0.89 mmol)Drop the reaction temperature will rise to room temperature,Heated to 70 C,Reaction 6h,The reaction was quenched with 10 mL of water and extracted with ethyl acetate (3 x 7 mL). Column chromatography (Petroleum ether: ethyl acetate = 10: 1) to give 0.17 g of a white solid, 86% yield, mp 180-182 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68.3% | With pyridine; chlorine; trichlorophosphate; at 100℃; for 5h; | In a reactor equipped with exhaust gas absorption, 27.0 g of benzoxazolone (molecular weight 135.1, 0.20 mol) was added, 150.0 g of phosphorus oxychloride (molecular weight 153.3, 0.98 mol), 79.1 g of pyridine (molecular weight 79.1, 1.0 mol), Stir and heat to about 100 ° C, Passing chlorine gas reaction, About 5g of chlorine gas is introduced every hour. Chlorine gas is about 5h, sampling and testing, 6-chlorobenzoxazolone content is less than 1percent as the end of the reaction; Atmospheric distillation, Removing the remaining phosphorus oxychloride; Vacuum distillation, Heating temperature is about 120 °C, Oil pump decompression, The degree of vacuum is 1~3Kpa, The product was isolated 25.7 g, White crystal, The yield is 68.3percent. The qualitative content is 99percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | General procedure: To a stirred suspension of benzo [d]oxazol-2(3H)-one derivative,or benzimidazole, or 2H-benzo [b] [1,4]oxazin-3(4H)-one(1.0 mmol), anhydrous K2CO3 (1.2 mmol) was added in the DMFsolvent for 20 min at 70 C. Then bromoacetylated 1a-1f or 2a-2c(1.3 mmol) and TBAI (0.1 mmol) were added simultaneously. Thereaction was stirred and heated for 4 h. After completion, themixture was extracted with EtOAc/H2O three times. The combinedorganic layers were washed with brine, dried over anhydrousNa2SO4, filtered and concentrated under reduced pressure. Thecrude product was purified by silica gel column chromatographyeluting with EtOAc/PE (3:1e8:1) to afford compounds B01-B29,C01-C03. |
Tags: 2-Benzoxazolinone | 2-Benzoxazolone | Carbamates | Antiparasitic | Secale | Natural Products-Other Structure | Organic Building Blocks | Anti-Infection | Poaceae | By Structure | 59-49-4
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