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Dimethylformamide → HCID 66690761, compound

HRID 592319
Notes
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Reaction equation

HRID 592319 reaction equation
[NH2:1][C:2]1[C:11]([N+:12]([O-:14])=[O:13])=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1Br.[F:16][C:17]1[CH:22]=[CH:21][C:20](B(O)O)=[CH:19][CH:18]=1.C(NC(C)C)(C)C.CN(C)C=O>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.[Na+].[Na+].[Na+].P(C1C=C(S([O-])(=O)=O)C=CC=1)(C1C=C(S([O-])(=O)=O)C=CC=1)C1C=C(S([O-])(=O)=O)C=CC=1.C(OCC)(=O)C.O>[NH2:1][C:2]1[C:3]([C:20]2[CH:21]=[CH:22][C:17]([F:16])=[CH:18][CH:19]=2)=[CH:4][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:10][C:11]=1[N+:12]([O-:14])=[O:13]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

9

Reactant 4

HCID 6228DimethylformamideHCID 7912DiisopropylamineHCID 2856454-Fluorophenylboronic acidHCID 13685347Methyl 4-amino-3-bromo-5-nitrobenzoate

Product 1

HCID 66690761HCID 66690761, compoundYield 88%

Reagents, catalysts & solvents 4

HCID 167845
palladium(II) acetate
Catalyst
HCID 6099338Trisodium 3,3',3''-phosphinetriyltris(benzene-1-sulphonate)Catalyst
HCID 962WaterSolvent
HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of methyl 4-amino-3-bromo-5-nitrobenzoate (1.0 g, 3.64 mmol), (4-fluorophenyl)-boronic acid (0.76 g, 5.45 mmol), 3,3′,3″-phosphinidynetris (benzensulfonic acid) trisodium salt (0.18 g, 0.27 mmol), palladium(II) acetate (20.0 mg, 0.09 mmol) and diisopropylamine (0.52 mL, 3.64 mmol) were added N,N-dimethylformamide (13.6 mL) and water (4.5 mL). The mixture was heated to 80° C. After 1 h, the mixture was cooled to ambient temperature and ethyl acetate was added. The organic layer was dried over magnesium sulfate, filtered and concentrated. Purification by silica gel chromatography (100% hexanes→50% hexanes/ethyl acetate) gave the title compound (0.93 g): LC-MS [M+1]=291.2.

Workup

  1. temperaturethe mixture was cooled to ambient temperature
  2. dry with materialThe organic layer was dried over magnesium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customPurification by silica gel chromatography (100% hexanes→50% hexanes/ethyl acetate)

Sources & evidence

ORD record
ord-507ec2e287054d22a392ae0df278dd3c
Source dataset
uspto-grants-2016_01
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US09238647B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes