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Chemical Structure| 312537-44-3 Chemical Structure| 312537-44-3

Structure of 312537-44-3

Chemical Structure| 312537-44-3

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Product Details of [ 312537-44-3 ]

CAS No. :312537-44-3
Formula : C26H18BrNO2
M.W : 456.33
SMILES Code : O=C1OC2=CC(Br)=CC=C2N1C(C3=CC=CC=C3)(C4=CC=CC=C4)C5=CC=CC=C5

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Application In Synthesis of [ 312537-44-3 ]

* 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 [ 312537-44-3 ]

[ 312537-44-3 ] Synthesis Path-Downstream   1~3

  • 1
  • [ 19932-85-5 ]
  • [ 76-83-5 ]
  • [ 312537-44-3 ]
YieldReaction ConditionsOperation in experiment
91% With triethylamine; In dichloromethane; at 20℃; for 18h; To a solution of 6-bromo-3H-benzoxazol-2-one (15 g; ca. 0.07 mol, containing 8-9% 3H-benzooxazol-2-one) and triethylamine (11.1 mL, 0.08 mol) in DCM (250 mL) was added trityl chloride (21.5 g, 0.08 mol). The solution was stirred at room temperature for 18 h and was then washed with distilled water (3×250 mL), brine (250 mL) and dried (MgSO4), filtered and evaporated to give an off-white colored solid. The product was dissolved in refluxing EtOAc then allowed to cool to room temperature with constant stirring for several hours. The solids were collected (21.16 g) and the filtrate was concentrated until precipitation occurred, re-heated (reflux) for several hours and allowed to cool with stirring to encourage a second crystallization (7.88 g). NMR and HPLC indicated the product (29.04 g, 91%) was very clean.
89% With triethylamine; In dichloromethane; at 20℃; To a solution of XXXV-2b (500 mg, 2.97 mmol) in dry DCM (20 mL) was added TEA (360 mg, 3.56 mmol) and Trt-Cl (992 mg, 3.56 mmol). The mixture was stuffed overnight at rt, then poured into water, extracted with DCM (50 mLx3). The combined organic layer was washed with brine, dried over anhydrous Na2SO4, and concentrated in vacuo. The residue was purified by column chromatography on silica gel (PE/EA=10/1) to afford XXXV-3b (1.2 g, 89% yield).
77% With NaH; In N,N-dimethyl-formamide; EXAMPLE 121 6-Bromo-3-trityl-3 H-benzooxazol-2-one 6-Bromo-3H-benzooxazol-2-one (0.165 g, 0.77 mmol) was added portionwise into a 0 C. suspension of NaH (44.8 mg, 1 mmol, 55%) in dry DMF (4 ml). After 1 hour stirring at room temperature, a solution of triphenylmethylchloride (0.24 g, 0.85 mmol) in DMF (0.5 ml) was added. The reaction mixture was stirred 1 hour at room temperature then quenched with H2O (15 ml). The aqueous phase was extracted with ethyl acetate, the combined organic phases were washed with H2O and brine, dried over Na2SO4 and concentrated to provide 6-bromo-3-trityl-3H-benzooxazol-2-one (0.27 g, 77%) as a beige solid, MS: Mm/e=457.1 (M+H+).
With triethylamine; In dichloromethane; at 20℃; for 18h; To a solution of 6-bromo-3H-benzoxazol-2-one (15 g; ca. 0.07 mol, containing 8-9% 3H-benzooxazol-2-one) and triethylamine (11.1 mL, 0.08 mol) in DCM (250 mL) was added trityl chloride (21.5 g, 0.08 mol). The solution was stirred at room temperature for 18 h and was then washed with distilled water (3 x 250 mL), brine (250 mL) and dried (MgSO4), filtered and evaporated to give an off-white colored solid. The product was dissolved in refluxing EtOAc then allowed to cool to room temperature with constant stirring for several hours. The solids were collected (21.16 g) and the filtrate was concentrated until precipitation occurred, re-heated (reflux) for several hours and allowed to cool with stirring to encourage a second crystallization (7.88 g).
2.0 g With triethylamine; In dichloromethane; for 1.16667h; [0156j Triethylamine (0.72 g, 1.0 mL, 7.1 mmol) was added to a stirring a mixture of 6- bromo-2benzoxazilinone (0.89 g, 4.2 mmol) and trityichioride (1.21 g, 4.4 mmol) in CH2C12 (10 mL) for a period of 10 mm. The reaction was monitored by TLC (silica gel) and concentrated after 1 h. The concentrate was diluted with water and sonicated to form a heterogeneous solution. The resulting off-white solid was suction filtered and dried to provide 1 -trityl-6-bromo-2- benzoxazilinone (2.0 g). LCMS: rt 9.45 mm (A), purity 96 %, MS (mle) 456 (MHj.

  • 2
  • [ 312537-44-3 ]
  • [ 503184-35-8 ]
  • C33H26N2O3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate; In 1,2-dimethoxyethane; water;Reflux; Compound 564 was prepared from XXXV-3b following the synthetic schemedescribed above. ?H NMR (400MHz, CDC13) (57.26-7.23 (m, 1H), 7.10 (s, 1H), 7.06-7.00 (m, 2H),6.49 (s, 1H), 3.92 (q, J=7.2Hz, 2H), 2.13 (s, 3H), 1.42 (t, J=7.2Hz, 3H). MS (ES) m/z [M+H]+270.9
  • 3
  • [ 312537-44-3 ]
  • [ 452972-11-1 ]
  • 6-(2-chloropyridin-3-yl)benzo[d]oxazol-2(3H)-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
With tetrakis(triphenylphosphine) palladium(0); water; sodium carbonate; In 1,4-dioxane; at 100℃; for 12h;Inert atmosphere; General procedure: [0150j A single necked round bottom flask (250 mL) equipped with a magnetic stir bar was charged with tert-butyl 5-bromo-1H-indazole-carboxylate (4.0 g, 13.4 mmol) dissolved in 1,4- dioxane (130 mL), 2-chloro-3-pyridine boronic acid pinacol ester (4 g, 16.7 mmol), Pd(PPh3)4 (1.5 g, 1.3 mmol) and 2M aq. Na2CO3 (20 mL, 40 mmol) under nitrogen atmosphere. The rubber septum was replaced with reflux condenser containing three-way stopcock equipped with argon filled balloon. The reaction contents were stirred and air was removed from the closed reaction system by vacuum and back filled with argon. Following three cycles of degassing, the reaction mixture was heated at 100 C (oil-bath) under argon. Inflated argon balloon was emptied, refilled with argon and remounted in the course of reaction. The initial pale yellow heterogeneous reaction mixture turned to clear biphasic off-brown solution. After 18 h with no additional change in the proportion of the product (62%) as analyzed by LC/MS, the reaction mixture was cooled to room temperature. Upon concentration of the reaction mixture, EtOAc/water (200 mL / 75 mL) was transferred to the concentrate and stirred for 30 mm. The organic layer was separated and the aqueous layer extracted with EtOAc (100 mL X 2). Mg504 (20 g) and Celite (20 g) were added to combined organic layers and the contents suction filtered after stirring for 1 h. The filter cake was washed with EtOAc (300 mL) and the combined filtrates concentrated by rotary evaporator under vacuum. The crude concentrate was dissolved in in 1% MeOH/CH2C12 and absorbed on silica gel (20 g) by evaporating the solvent followed by drying. Subsequent purification by flash silica gel columnpurification of the dry powder (Combiflash companion system with RediSep silica gel column 120 g, 30-70%EtOAC/hexanes eluting solvent) provided 5-(2-chloropyridin-3-yl)-1H-indazole (1.5 g, 47%) as a white crystalline solid after concentration of the desired product fractions. [01 57j Analogous to the preparation of 5 -(2-chloropyridin-3 -yl)- 1 H-indazole,6-(2- chloropyridin-3 -yl)benzo [d]oxazol-2(3H)-one was prepared by heating the mixture of 1 -trityl-6- bromo-2-benzoxazilinone (2.0 g, 4.4 mmol), 2-chloro-3-pyridine boronic acid pinacol ester (1.3 g, 5.4 mmol), Pd(PPh3)4 (0.5 g, 0.43 mmol) and 2M aq. Na2CO3 (8 mL, 16 mmol) in 1,4-dioxane (75 mL) under argon atmosphere for 12 h. LC/MS indicated three products with MH 489, 245 and 566. Extractive work-up followed by flash silica gel column purification (Combiflash companion system with RediSep silica gel column 40 g , 20-70%EtOAC/hexanes eluting solvent gradient upon dry loadingthe concentrate absorbed on silica gel) provided 6-(2- chloropyridin-3-yl)benzo[d]oxazol-2(3H)-one (0.44 g, 38%) as an off-white solid after concentration of the respective product fractions. LCMS: rt 5.85 mm (A), purity 94 %, MS (mle) 247 (MHj.
 

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