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Chemical Structure| 446864-55-7 Chemical Structure| 446864-55-7

Structure of 446864-55-7

Chemical Structure| 446864-55-7

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Product Details of [ 446864-55-7 ]

CAS No. :446864-55-7
Formula : C8H4BrNO
M.W : 210.03
SMILES Code : N#CC1=CC=CC(C=O)=C1Br
MDL No. :MFCD18206376
InChI Key :PHZMJSCJHNIUSL-UHFFFAOYSA-N
Pubchem ID :22265572

Safety of [ 446864-55-7 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H312-H332
Precautionary Statements:P261-P264-P270-P271-P280-P301+P312-P302+P352-P304+P340-P330-P363-P501

Application In Synthesis of [ 446864-55-7 ]

* 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 [ 446864-55-7 ]

[ 446864-55-7 ] Synthesis Path-Downstream   1~1

  • 1
  • [ 1086429-88-0 ]
  • [ 446864-55-7 ]
YieldReaction ConditionsOperation in experiment
84.2% With silica gel; pyridinium chlorochromate; In dichloromethane; at 20℃; for 2.0h; General procedure: To the solution of 23 (26.0 g, 0.103 mol) in THF/MeOH/H2O (55:50:100 mL) was added LiOH?H2O (17.3 g, 0.411 mol, 4 equiv). The mixture was stirred for 1 h and concentrated. DCM was added. The organic layer was washed with 1 N HCl, saturated NaHCO3, brine, dried over anhydrous Na2SO4, filtered and concentrated. The residue was washed with PE to give the product 51 (16.2 g, yield 80%). To the mixture of 51 (14.2 g, 67 mmol) and silica gel (14.2 g) in DCM (268 mL) was added PCC (21.6 g, 0.1005 mol, 1.5 equiv). The mixture was stirred for 2 h. The reaction mixture was filtered and the filtrate was concentrated. The residue was purified by silica gel chromatography to give the desired product 52 (11.8 g, 84.2%) as a solid. To the solution of 52 in DMSO (75 mL) were added Ph3PCH2OMe chloride (29.4 g, 3.6 equiv) in DMSO (75 ml) and t-BuOK (9 g, 3.4 equiv) in one portion. The mixture was stirred for 1 h at rt and 52 (5 g, 1 equiv) in DMSO (50 mL) was added in one portion at 0 C, and then stirred overnight. The reaction solution was poured into water, extracted with EA, washed with brine, dried over Na2SO4, filtered and evaporated. The residue was purified by silica gel column to give 53 (4.1 g, yield 72%) as a yellow solid. TLC (silica gel plate, PE/EA = 10:1): Rf = 0.45. To the solution of 53 (2 g, 8.37 mmol) in THF (42 mL) was added HCl (6 N, 14 mL) at rt and the reaction was refluxed for 1 h. The reaction was cooled, poured into water, extracted with EA, washed with water, brine, dried over anhydrous Na2SO4 and evaporated to give 54 (2.54 g) as crude oil. TLC (silica gel plate, PE/EA = 10:1): Rf = 0.2. To the solution of 54 (2.54 g) in methanol (20 mL) was added NaBH4 (319 mg, 1 equiv) in portions for 10 min. The solution was stirred for 1 hand water (50 mL) was added for 10 min. The solution was extracted with EA, washed with water, dried over Na2SO4 and evaporated to give 55 (2.41 g) as crude oil. TLC (silica gel plate, PE/EA = 3:1): Rf = 0.3. To the solution of 55 (2.41 g) and Et3N (1.2 g, 1.1 equiv) in DCM (35 mL) was added acetyl chloride (0.84 g, 1 equiv) dropwise at 0 C. The reaction wasstirred at 0-C for 2 hand water (50 mL) was added to the reaction solution. The solution was extracted with EA and the organic layer was washed with brine, dried over anhydrous Na2SO4 andevaporated. The residue was purified by silica gel column (PE/EA = 10:1) to give the product 56 (2.2 g, 98% of three steps). 1HNMR(300 MHz, CDCl3): delta 7.57 (d, 1H), 7.48 (d, 1H), 7.37 (t, 1H), 4.32 (t, 2H), 3.15 (t, 2H), 2.03 (s, 1H) ppm. To the mixture of 56 (1 g), pin2B2 (1.04 g, 1.1 equiv) and KOAc (0.73 g, 2 equiv) in 1,4-dioxane (20 mL) was added Pd(dppf)Cl2 (100 mg, 5% equiv) under N2. The reaction was refluxed for 2 h. The reaction solution was cooled to rt, poured into water (50 mL) and extracted with EA. The organic phase was washed with water, brine, dried over anhydrous Na2SO2 and concentrated. The residue was purified by silica gel column (PE/EA = 10:1) to give 57 (0.9 g) as a colorless oil. TLC (silica gel plate, PE/EA = 3:1): Rf = 0.7. To the solution of 57 (1 g) in MeOH (20 mL) was added NaOH (0.254 g, 2 equiv) in one portion at 0 C. The reaction solution was stirred at rt for1 h. MeOH was rotary evaporated to give a residue that was mixed with HCl (6 N, 1.1 mL). The reaction was stirred overnight, quenched with NaOH (1 N, 10 mL), washed with EA. The aqueous phase was acidified with HCl (1 N) to pH 1-2 and extracted with EA. The combined organic layer was washed with brine, dried over Na2SO4, and evaporated to give 58 (540 mg, yield 51%) as a white solid. 1H NMR (300 MHz, DMSO-d6): delta 8.84 (s, 1H), 7.67 (d, 1H), 7.54 (m, 2H), 4.07 (t, 2H), 2.94 (t,2H). MS: m/z = 174 (M+1, ESI+). To the solution of 58 (540 mg, 3.12 mmol) in HCOOH/water (5.4:0.54 mL) was added Raney Ni. The reaction was stirred at 100 C for 1 h, cooled to rt, quenched with water and extracted with EA. The organic phase was washed with water, brine, dried over Na2SO4, and concentrated. The residue was purified by silica gel column (PE/EA = 3:1) to give 59 (460 mg, 85%) as a white solid. 1H NMR (300 MHz, DMSO-d6): delta 10.69 (s, 1H), 9.01 (s, 1H), 7.74 (q, 1H), 7.54 (m, 2H), 4.09 (t, 2H), 2.96 (t, 1H) ppm. MS:m/z = 177(M+1, ESI+). To the solution of Ph3PCH2COOCH2CH3 bromide in THF (6 mL) was added NaH (60%, 68 mg, 3 equiv). The reaction was stirred under N2 for 1 h at rt. Compound 59 (100 mg, 1 equiv) in THF (2 mL) was added in one portion at 0 C. The mixture was stirred overnight, quenched with water (10 mL) and HCl (1 N 10 mL), extracted with EA. The organic phase was washed with brine, dried over Na2SO4 and concentrated. The residue was purified by silica gel column (PE/EA = 10:1-3:1) to give 60 (140 mg, yield 98%) as a white solid. 1H NMR (300 MHz, DMSO-d6): delta 8.73 (s, 1H), 8.70 (d, 1H), 7.70 (d, 1H), 7.42 (t, 1H), 7.26 (d, 1H), 6.45 (d, 1H) 4.30 (q, 2H), 4.03 (t, 2H), 2.89 (t, 2H), 1.20 (t, 3H) ppm. MS: m/z = 255 (M+23, ESI+). T...
 

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Technical Information

• Alkyl Halide Occurrence • Barbier Coupling Reaction • Baylis-Hillman Reaction • Benzylic Oxidation • Birch Reduction • Blaise Reaction • Blanc Chloromethylation • Bucherer-Bergs Reaction • Catalytic Hydrogenation • Clemmensen Reduction • Complex Metal Hydride Reductions • Corey-Chaykovsky Reaction • Corey-Fuchs Reaction • Fischer Indole Synthesis • Friedel-Crafts Reaction • General Reactivity • Grignard Reaction • Hantzsch Dihydropyridine Synthesis • Henry Nitroaldol Reaction • Hiyama Cross-Coupling Reaction • Horner-Wadsworth-Emmons Reaction • Hydride Reductions • Hydrogenolysis of Benzyl Ether • Julia-Kocienski Olefination • Kinetics of Alkyl Halides • Knoevenagel Condensation • Kumada Cross-Coupling Reaction • Leuckart-Wallach Reaction • McMurry Coupling • Meerwein-Ponndorf-Verley Reduction • Mukaiyama Aldol Reaction • Nozaki-Hiyama-Kishi Reaction • Passerini Reaction • Paternò-Büchi Reaction • Petasis Reaction • Pictet-Spengler Tetrahydroisoquinoline Synthesis • Preparation of Aldehydes and Ketones • Preparation of Alkylbenzene • Preparation of Amines • Prins Reaction • Reactions of Aldehydes and Ketones • Reactions of Alkyl Halides with Reducing Metals • Reactions of Amines • Reactions of Benzene and Substituted Benzenes • Reactions of Dihalides • Reformatsky Reaction • Ritter Reaction • Schlosser Modification of the Wittig Reaction • Schmidt Reaction • Stetter Reaction • Stille Coupling • Stobbe Condensation • Substitution and Elimination Reactions of Alkyl Halides • Suzuki Coupling • Tebbe Olefination • Thorpe-Ziegler Reaction • Ugi Reaction • Vilsmeier-Haack Reaction • Wittig Reaction • Wolff-Kishner Reduction

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