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Chemical Structure| 40887-80-7 Chemical Structure| 40887-80-7

Structure of 40887-80-7

Chemical Structure| 40887-80-7

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Product Details of [ 40887-80-7 ]

CAS No. :40887-80-7
Formula : C6H7BrN2
M.W : 187.04
SMILES Code : NNC1=CC=CC(Br)=C1
English Name :(3-Bromophenyl)hydrazine
MDL No. :MFCD02656654

Safety of [ 40887-80-7 ]

Application In Synthesis of [ 40887-80-7 ]

* 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 [ 40887-80-7 ]

[ 40887-80-7 ] Synthesis Path-Downstream   1~10

  • 1
  • [ 24424-99-5 ]
  • [ 79099-07-3 ]
  • [ 40887-80-7 ]
  • [ 1173155-30-0 ]
YieldReaction ConditionsOperation in experiment
42% Stage #1: N-tert-butyloxycarbonylpiperidin-4-one; 3-bromophenylhydrazine With hydrogenchloride In ethanol; water for 18h; Reflux; Stage #2: di-<i>tert</i>-butyl dicarbonate With dmap; triethylamine In dichloromethane at 20℃; for 18h; 1.a 3-Bromophenylhydrazine (40.0 g, 0.179 mol) and JV-Boc-4-oxo-piperidine (35.4 g, 0.179 mol) were dissolved in ethanol (368 mL), and cone. HCl (72 mL) was added. The reaction mixture was then heated to reflux for 18 h, concentrated and basifed using 10% NH4OH in methanol (10%, 100 mL). The solvent was removed, and the residue was suspended in CH2Cl2 (1.2 L). BoC2O (39.2 g, 0.179 mol) followed by DMAP (195 mg, 1.6 mmol) and Attorney's Docket 2882.023B triethylamine (46.4 niL, 0.358 mol) were then added, and the reaction progressed at room temperature for 18 h. The mixture was washed with 0.5 N HCl, and the organic phase was removed, dried over Na2SO4, filtered and concentrated to dryness. The resulting mixture of regioisomers was purified by flash column chromatography (silica gel, hexanes/EtOAc, 100:0 to 80:20 to 50:50 then 25:75) to give the more polar title compound (26.2 g, 42%) as a yellow solid: 1H NMR (300 MHz, CDCl3) δ 8.16 (br s, IH), 7.42 (s, IH), 7.28 (d, J= 8.1 Hz, IH, partially masked by solvent), 7.18 (d, J= 8.1 Hz, IH), 4.60 (s, 2H), 3.80 (t, J= 5.5 Hz, 2H), 2.79 (t, J= 5.6 Hz, 2H), 1.51 (s, 9H).
  • 2
  • [ 13395-36-3 ]
  • [ 40887-80-7 ]
  • [ 784142-85-4 ]
  • C16H19BrN2O2 [ No CAS ]
  • 3
  • [ 40887-80-7 ]
  • [ 870552-47-9 ]
  • [ 158326-84-2 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: triethylamine / dichloromethane / 20 °C 2: calcium hydride / 180 - 230 °C
  • 4
  • [ 104618-32-8 ]
  • [ 40887-80-7 ]
  • [ 1342949-97-6 ]
YieldReaction ConditionsOperation in experiment
In ethanol; at 20℃; for 5h; To a solution of commercially available 3-bromophenyl hydrazine (2.74 g, 12.2 mmol) in ethanol (100 mL) was added ketone derivative (3 g, 12.2 mmol) in ethanol (50 mL). The reaction mixture was stirred for 5 h at room temperature. The solvent was removed to give the title compound as a solid (5 g, quantitative). The product was used in the next step without any purification.
  • 5
  • [ 84719-31-3 ]
  • [ 40887-80-7 ]
  • [ 1352837-23-0 ]
YieldReaction ConditionsOperation in experiment
With water In diphenylether at 232℃; for 4h; Dean-Stark apparatus; 39.1 Example 39; 7-(2-Hydroxypropan-2-yl)- 1 -(2-methyl-3 -(4-oxoquinazolin-3 (4H)-yl)phenyl)-5H- pyrido[4,3-b]indole-4-carboxamide 1. 7-Bromo-2,5-dihydro-lH-pyrido[4,3-b]indol-1-one; (3-Bromophenyl)hydrazine HCl (20.5730 g, 92.4 mmol) was dissolved in 6.25 N aqueous NaOH (16 mL, 100 mmol), ethanol (80 mL) and water (60 mL), and extracted with EtOAc (200 mL). The organic layer was dried over MgSO4, filtered andconcentrated in vacuo. CH2CL2 (150 mL) was added, dried over MgSO4, filtered and concentrated in vacuo to give (3-bromophenyl)hydrazine as a light orange oil. To a heterogeneous solution of (3-bromophenyl)hydrazine (17.19 g, 92 mmol) in Phenyl ether (82 mL) was added pyridine-2,4-diol (5.11 g, 46.0 mmol). A Dean-Stark trap was set up, and the reaction was heated at 232 °C for 4 hours. A strong effervescence and gas evolution occurred often for 45 min. The solution turned homogeneous with decrease in frequency of strong effervescence and gas evolution. The reaction mixture was cooled to room temperature; precipitation ensued. HPLC and LCMS showed completion of reaction (86784-071-01). Toluene (100 mL) was added, and the mixture stirred overnight at room temperature. The mixture was filtered and the precipitate was collected. Methanol (40 mL) was added, and the solution was stirred for 20 min. The precipitate was filtered and washed with methanol, dried to give 7-bromo-2,5-dihydro-1H-pyrido[4,3-b]indol-1- one as a tan solid. Methanol (60 mL) was added, and the mixture was stirred for 7 h. The precipitate was collected to give 7-bromo-2,5-dihydro-1H-pyrido[4,3-b]indol-1-one (4.4374 g, 16.87 mmol, 36.7% yield) a light tan solid. The precipitate was collected to give 7-bromo-2,5-dihydro-1H-pyrido[4,3-b]indol-1-one (4.4374 g, 16.87 mmol, 36.7% yield) a light tan solid. The product had an HPLC Retention Time = 2.585 min[mixture of rotamers] [4min grad, 10%MeOH/water to 90%MeOH/water, 0.1%TFA, YMCCOMBISCREEN ODS-A, 4.6x50mm, 220nM; LC/MS +1 263.04;265.04
  • 6
  • [ 40887-80-7 ]
  • [ 1173155-30-0 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: hydrogenchloride / ethanol; water / 18 h / Reflux 2: dmap; triethylamine / dichloromethane / 18 h / 20 °C
  • 7
  • [ 126-81-8 ]
  • [ 40887-80-7 ]
  • [ 1301219-07-7 ]
YieldReaction ConditionsOperation in experiment
18% With trifluoroacetic acid at 140℃; for 0.166667h; Microwave irradiation; 5.1 Step 1. Synthesis of 7-bromo-2,2-dimethyl-2,3-dihydro-lH-carbazol-4(9H)-on)[formula 1-2] Step 1. Synthesis of 7-bromo-2,2-dimethyl-2,3-dihydro-lH-carbazol-4(9H)-on)[formula 1-2]To a microwave vial were added 3-bromophenyl hydrazine [formula 1-1] (0.17 g, 0.76 mmol), 5-5-dimethyl-l,3-cyclohexandion (0.12 g, 0.85 mmol) and TFA(1 mL), and a reaction was carried out in a microwave reactor at 140°C for 10 minutes. Then, the reaction mixture was extracted with ethyl acetate and saturated NaHC03 aqueous solution; the organic layer was washed with brine, dried over anhydrous Na2S04, filtered and concentrated under reduced pressure. Residue was purified by column chromatography (Si02; hexane/ethylacetate, 4/1) to yield the title compound (0.04 g, 18%).
18% With trifluoroacetic acid at 140℃; for 0.166667h; Microwave irradiation; 5.1 Step 1. Synthesis of 7-bromo-2,2-dimethyl-2,3-dihydro-1H-carbazol-4(9H)-on) [formula 1-2] To a microwave vial were added 3-bromophenyl hydrazine [formula 1-1] (0.17 g, 0.76 mmol), 5-5-dimethyl-1,3-cyclohexandion (0.12 g, 0.85 mmol) and TFA (1 mL), and a reaction was carried out in a microwave reactor at 140° C. for 10 minutes. Then, the reaction mixture was extracted with ethyl acetate and saturated NaHCO3 aqueous solution; the organic layer was washed with brine, dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. Residue was purified by column chromatography (SiO2; hexane/ethylacetate, 4/1) to yield the title compound (0.04 g, 18%).
  • 8
  • [ 84719-31-3 ]
  • [ 40887-80-7 ]
  • [ 1352837-23-0 ]
  • [ 1820964-31-5 ]
YieldReaction ConditionsOperation in experiment
27.1% Stage #1: 3-deazauracil; 3-bromophenylhydrazine In diphenylether at 175 - 230℃; for 3h; Dean-Stark; Inert atmosphere; Stage #2: In methanol for 0.5h; Sonication; 1 Intermediate 1A In a 50 mL round-bottomed flask equipped with a Dean-Stark were added (3-bromophenyl)hydrazine free- base (3.20 g, 17.11 mmol) and pyridine-2,4-diol (1 g, 9.00 mmol) in diphenyl ether (15.75 ml) under N2 (3 cycles vacuum then refill with N2). The mixture was heated to 175°C for ca. 20 minutes, then gradually to 230°C and stirred for 3 hours. The biphasic mixture was cooled to 100°C and toluene (25 ml) was added. The resulting slurry was stirred at 20°C for 1 hour and the solids were collected on Buchner. The cake was washed with toluene (3 x 5 mL) and the product dried at 20°C under high vacuum to give 2.05 g as a tan solid containing two isomers. The solids were ground to a fine solid and sonicated in MeOH (5 mL) for 15 minutes and collected again on Buchner. This furnishedd 761 mg of the product containing ca. 10% of the 9-bromo isomer. This sequence was repeated to give 7-bromo-5H-pyrido[4,3-b]indol-1-ol (642 mg, 2.4 mmol, 27.1 % yield) as a tan solid. 1H NMR (400 MHz, DMSO-d6) ö ppm 6.52 (d, J=7.0 Hz, 1 H) 7.29 - 7.37 (m,2H) 7.67 (d, J=1.6 Hz, 1 H) 8.00 (d, J=8.6 Hz, 1 H)11.13- 11.23(m, 1 H)11.82(s, 1 H).
  • 9
  • [ 84719-31-3 ]
  • [ 40887-80-7 ]
  • [ 1352837-23-0 ]
YieldReaction ConditionsOperation in experiment
In diphenylether at 235℃; for 6h; 2.1 Step 1: 7-bromo-5H-pyrido [4,3 -bi indol- 1 -ol Into a 10000-mL 4-necked round-bottom flask was placed a solution of pyridine2,4-diol (500 g, 4.50 mol, 1.00 equiv) in phenyl ether (4000 mL), and (3-bromophenyl)hydrazine (1675 g, 8.96 mol, 2.00 equiv). The resulting solution was stirred for 6 h at 23 5°C. The resulting solution was cooled and diluted with 2000 mL of methylbenzene. The solids were collected byfiltration to provide 7-bromo-5H-pyrido[4,3-bjindol-1-ol as a solid.
  • 10
  • [ 24424-99-5 ]
  • [ 41979-39-9 ]
  • [ 40887-80-7 ]
  • [ 1173155-30-0 ]
  • [ 2056247-62-0 ]
YieldReaction ConditionsOperation in experiment
Stage #1: 4-piperidone hydrochloride; 3-bromophenylhydrazine With hydrogenchloride In 1,4-dioxane; isopropyl alcohol for 18h; Reflux; Stage #2: di-<i>tert</i>-butyl dicarbonate With triethylamine In dichloromethane at 20℃; for 18h; 1.1; 1.2 Step 2: ferf-butyl 7-bromo-1 ,3,4,5-tetrahydropyrido[4,3-b]indole-2-carboxylate Step 1 : 7-bromo-2,3,4,5-tetrahydro-1 H-pyrido[4,3-b]indole and 9-bromo-2,3,4,5- tetrahydro-1 H-pyrido[4,3-b indole: To a solution of (3-bromophenyl)hydrazine (10.Og, 53.5mmol) in IPA (1 OOmL) was added piperidin-4-one HCI (7.9g, 58.8mmol) and HCI (40ml_ of a 4.0M solution in dioxane). The reaction mixture was heated to reflux for 18 hours. The reaction mixture was cooled, filtered and rinsed with I PA to afford the intermediate HCI salt as a mixture of regio-isomers. LC-MS (m/z): [M+H] = 251 , 253. Step 2: ferf-butyl 7-bromo-1 ,3,4,5-tetrahydropyrido[4,3-b]indole-2-carboxylate To a mixture of 7-bromo-2,3,4,5-tetrahydro-1 H-pyrido[4,3-b]indole and 9-bromo-2,3,4,5- tetrahydro-1 H-pyrido[4,3-b]indole (12.5g, 43.5mmol) in CH2CI2 (150mL) was added triethylamine (18.4ml_, 130.0mmol) followed by boc anhydride (8.3g, 47.8mmol). The reaction mixture was stirred at room temperature for 18 hours. Water was added to the reaction mixture and the organic phase was separated, washed with brine, dried (Na2S04), and concentrated under vacuum. The crude mixture was chromatographed (220gRedi-Sep column) eluting from 100% hexanes to 25:75 EtOAc:hexanes, collecting the title compound as first eluting peak. LC-Ms (m/z): [M+H-ibutyl] = 295, 297. The second eluding peak constituted the 9' regio-isomer
 

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