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HuagongsheHuagongshe Chemistry Print Report · For research reference only
HRID 241198Generated: October 31, 2026

1,4-Dioxane → HCID 178433184, compound

https://huagongshe.com/reaction/241198

Reaction equation

Participants

RoleNameHCIDCharge
Reactant1,4-DioxaneHCID 31275—
ReactantDiisopropylethylamineHCID 81531—
Reactant(4-{5-[(4-Fluorophenyl)methyl]-6-methylpyrimidin-4-yl}-2,3,4,5-tetrahydro-1,4-benzoxazepin-7-yl)boronic acidHCID 66820119—
ReactantIsobutyl 5-bromo-2-(2-fluoroethylamino)-1H-benzo[d]imidazole-1-carboxylateHCID 86647855—
CatalystBis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)HCID 178418228—
SolventWaterHCID 962—
SolventEthyl AcetateHCID 8857—
ProductHCID 178433184HCID 17843318425%

Reaction Conditions

Temperature95 °C

Reaction Steps

Isobutyl 5-bromo-2-(2-fluoroethylamino)-1H-benzo[d]imidazole-1-carboxylate (76 mg, 0.21 mmol) and (4-{5-[(4-fluorophenyl)methyl]-6-methylpyrimidin-4-yl}-2,3,4,5-tetrahydro-1,4-benzoxazepin-7-yl)boronic acid (example 8 step 2) (100 mg, 0.25 mmol), and [1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium(II) (8.5 mg, 0.01 mmol) were taken into dioxane (1 mL) and water (200 uL) followed by addition of DIPEA (180 uL, 1.03 mmol) and the mixture was heated to 95° C. over 12 h. On cooling to room temperature the crude mixture was diluted with ethyl acetate and dried over anhydrous sodium sulfate then filtered through a bed of silica gel. The filtrate was concentrated and the residue taken into methanol (5 mL) and basified by addition of 5 drops of 50% aqueous sodium hydroxide. The methanol solution was stirred for 0.5 h at room temperature then concentrated. The residue was partitioned with isopropyl acetate and 1M aqueous sodium hydroxide. The organic phase was washed twice with additional 1M aqueous sodium hydroxide then dried over anhydrous sodium sulfate, filtered and concentrated. The residue was purified by silica gel chromatography using 20:1 ethyl acetate:ethanol then 10% methanol in dichloromethane as eluent. Fractions containing pure material were concentrated and the residue triturated with ethyl ether. The suspension collected by filtration to give N-(2-fluoroethyl)-5-(4-{5-[(4-fluorophenyl)methyl]-6-methylpyrimidin-4-yl}-2,3,4,5-tetrahydro-1,4-benzoxazepin-7-yl)-1H-benzimidazol-2-amine (27.4 mg, 25% yield). 1H NMR (400 MHZ, DMSO-d6): 10.84 (br s, 1H), 8.50 (s, 1H), 7.34 (d, 1H), 7.26 (br s, 1H), 7.18 (d, 1H), 7.12 (d, 4H), 6.98-6.91 (m, 3H), 6.85 (s, 1H), 4.68 (m, 1H), 4.55 (m, 1H), 4.46 (s, 2H), 4.25 (br s, 2H), 4.01 (s, 2H), 3.77 (br s, 2H), 2.16 (s, 3H). MS (EI) for C30H28F2N6O: 528 (MH+).

Provenance & Evidence

DOI10.6084/m9.figshare.5104873.v1
Patent numberUS08648066B2
Source datasetuspto-grants-2014_02
ORD IDord-f9d49e2d179e4b6ebd8dbad197cf86b2
Source noteuspto-grants-2014_02