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Chemical Structure| 54903-15-0 Chemical Structure| 54903-15-0

Structure of 54903-15-0

Chemical Structure| 54903-15-0

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Product Details of [ 54903-15-0 ]

CAS No. :54903-15-0
Formula : C8H5NO3
M.W : 163.13
SMILES Code : O=CC1=CC=C2NC(OC2=C1)=O

Safety of [ 54903-15-0 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Application In Synthesis of [ 54903-15-0 ]

* 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.

  • Downstream synthetic route of [ 54903-15-0 ]

[ 54903-15-0 ] Synthesis Path-Downstream   1~3

  • 1
  • [ 19932-85-5 ]
  • [ 54903-15-0 ]
YieldReaction ConditionsOperation in experiment
0.6402 g (91%) With n-butyllithium; sec.-butyllithium; In tetrahydrofuran; N-methyl-acetamide; methanol; hexane; cyclohexane; water; 2-Oxo-2,3-dihydro-benzooxazole-6-carbaldehyde A solution of 6-bromo-3H-benzooxazol-2-one (0.9236 g, 4.31 micromoles) in anhydrous tetrahydrofuran (25 mL) and dimethylformamide (3 mL) under nitrogen was cooled to -78 C. before addition of n-butyllithium (2.5M in hexane) (3.8 mL, 2.2 equiv). After stirring for 10 min at -78 C., 24 mL of sec-butyllithium (1.4 M in cyclohexane, 8 equiv) was added. The reaction was stirred while slowly warming to -40 C. When this temperature was reached, the reaction was quenched by addition of methanol. The reaction mixture was concentrated in vacuo and water was added. The aqueous layer was acidified with 1N HCl (ca. pH 5) and extracted with ethyl acetate (3*50 mL), dried over sodium sulfate, filtered and concentrated to give the product, 0.6402 g (91%). MS (ESI) 164 (MH)+. 1H NMR (400 MHz, DMSO-d6) δ 9.90 (1H, s), 7.79 (1H, d, J=8.0 Hz), 7.74 (1H, s), 7.28 (1H, d, J=8.0 Hz).
  • 2
  • [ 19932-85-5 ]
  • [ 33513-42-7 ]
  • [ 54903-15-0 ]
YieldReaction ConditionsOperation in experiment
75.4% <strong>[19932-85-5]6-bromo-3H-1,3-benzoxazol-2-one</strong> (8A) (1.78g, 13 mmol) was dissolved in tetrahydrofuran (15 ml), and under N2 protection, a solution of 2M isopropyl magnesium chloride in tetrahydrofuran (7 mL, 14 mmol) were added at -10C. The temperature was raised to 0C, followed by reaction for 1 hour. A solution of n-butyllithium in tetrahydrofuran (21 ml, 52 mmol) was added at -25C, followed by reaction at -10C for 30 min. N,N-dimethylformamide (9.5 g, 130 mmol) was added at -10C, and the temperature was gradually raised to room temperature, followed by reaction for 0.5 hours. The reaction solution was poured into water (50 ml) containing 5 g citric acid, and was extracted by addition of ethyl acetate (50 ml). The aqueous phase was extracted with ethyl acetate (50 mL*1). The organic phases were combined. The organic phase was dried over anhydrous sodium sulfate and filtered.The filtrate was concentrated under reduced pressure, made into a slurry with 50% (v/v) ethyl acetate/petroleum ether, and purified by silica gel column chromatography (ethyl acetate/petroleum ether (v/v) = 0:1 to 1:4) to obtain the title compound 2-oxo-3H-1,3-benzoxazole-6-carbaldehyde (8B) as a white solid (1.60 g, yield 75.4%). 1H NMR (400 MHz, DMSO-d6) δ 12.16 (s, 1H), 9.92 (s, 1H), 7.78 (dd, 1H), 7.74 (d, 1H), 7.29 (d, 1H). LCMS m/z=164.1[M+1].
66% The bromo compound R (1.0 g, 4.67 mmol) was taken in an oven-dried RB equipped with magnetic stir-bar and dissolved in anhydrous THF (9 mL). The solution was cooled to -78 C. and MeMgBr (1.8 mL) was added slowly. The mixture was stirred for 45 min and anhydrous THF (37.5 mL) was added slowly to maintain the internal temperature at -50 C. After the solution was cooled back to -78 C., t-BuLi (10.6 mL, 9.8 mmol, 1.6 M in pentane) was added dropwise. Next, DMF (2.2 mL, 28.1 mmol) was added slowly to the yellow solution and the dry-ice bath was removed after 15 min. After 2 h, the reaction was quenched with water and the THF was removed under vacuo on a rotary evaporator. The residue was dissolved in ethyl acetate and washed with 1N HCl (5 mL). The organic layer was separated and the aqueous layer was extracted with ethyl acetate (3×5 mL). The organic layers were combined, dried over Na2SO4 and concentrated under vacuo on a rotary evaporator. The crude was first recrystallized from hexanes/ethyl acetate and then purified via gradient silica gel column chromatography using a mixture of hexanes and ethyl acetate (10:1 to 1:1) to obtain the desired aldehyde S as a white solid (500 mg, 66%). 1H NMR (500 MHz, CDCl3): δ 9.85 (s, 1H), 7.66 (dd, J=7.9 Hz, 1.2 Hz, 1H), 7.63 (s, 1H), 7.11 (d, J=7.9 Hz, 1H). 13C NMR (125 MHz, CDCl3): δ 190.9, 155.2, 144.1, 135.9, 131.4, 128.2, 109.6, 109.5
  • 3
  • [ 19932-85-5 ]
  • [ 75-16-1 ]
  • [ 54903-15-0 ]
YieldReaction ConditionsOperation in experiment
Intermediate 4. 2- oxo-2,3-dihydro-1 ,3-benzoxazole-6-carbaldehyde To a suspension of <strong>[19932-85-5]6-bromobenzo[d]oxazol-2(3H)-one</strong> (6.12g, 28.6mmol) in THF (60ml_) was added, at -78 C and under argon atmosphere, methylmagnesium bromide (10.6ml_ of a 3M solution in diethyl ether, 31 .8mmol) and the reaction mixture was stirred at this temperature fro 30 min. The, an additional amount of THF (240 mL) was added at a rate that the internal temperature was below -50 C. Then, tert-butyllithium (60.6ml_ of a 1.7 M solution in pentane, 103mmol) was slowly added and stirred for 45 min at -78 C. To the yellow suspension DMF (13.4ml_, 181 mmol) was then added, and the reaction mixtures was allowed to warm up to room temperature and stirring wasa continued for 3 additional hours. Water (300ml_) was then added to the crude mixture and the organic solvent was removed under reduced pressure. To the remaining aqueous phase, ethyl acetate (500ml_) and 1 N HCI (150ml_) were added and the the mixture was vigorously stirred and the organic phase was separated. The aqueous phase was further extracted with ethyl acetate (3 x 100 mL) and the combined organic extracts were washed with water, brine, dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to yield the title compound (4.75g, 96%, 94% purity by UPLC). The compound was used as this without further purification. LRMS (m/z): 162 (M-1 )-
 

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