Potassium Phosphate, Tribasic → N4-Methyl-3,3'-dinitrobiphenyl-4,4'-diamine

HRID 628577

Reaction equation

Br[C:2]1[CH:9]=[CH:8][C:5]([NH:6][CH3:7])=[C:4]([N+:10]([O-:12])=[O:11])[CH:3]=1.[N+:13]([C:16]1[CH:22]=[C:21](B2OC(C)(C)C(C)(C)O2)[CH:20]=[CH:19][C:17]=1[NH2:18])([O-:15])=[O:14].C1(C2C=CC=CC=2)C=CC=CC=1P(C1CCCCC1)C1CCCCC1.[O-]P([O-])([O-])=O.[K+].[K+].[K+]>COCCOC.O>[CH3:7][NH:6][C:5]1[CH:8]=[CH:9][C:2]([C:21]2[CH:20]=[CH:19][C:17]([NH2:18])=[C:16]([N+:13]([O-:15])=[O:14])[CH:22]=2)=[CH:3][C:4]=1[N+:10]([O-:12])=[O:11]

Participants

Conditions

Temperature: 130 °C

Procedure

4-Bromo-N-methyl-2-nitroaniline (100 mg, 0.43 mmol), 2-nitro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (115 mg, 0.43 mmol), biphenyl-2-yldicyclohexylphosphine (30 mg, 20 mol %) and K3PO4 (275 mg, 1.3 mmol) were suspended in DME-H2O (4:1, 5 mL), the mixture was purged with nitrogen then degassed by sonication. Pd(OAc)2 (5 mg, 5 mol %) was added, and the mixture heated to 130° C. for 10 min under microwave irradiation. The cooled mixture was diluted with EtOAc and H2O. The organics were separated and the aqueous layer extracted with EtOAc (3×50 mL). The combined organic extracts were washed with brine, dried (MgSO4), filtered and concentrated in vacuo to give the crude product as a dark brown solid (210 mg). The crude material was taken on without further purification.

Workup

customthe mixture was purged with nitrogen
customthen degassed by sonication
additionPd(OAc)2 (5 mg, 5 mol %) was added
additionThe cooled mixture was diluted with EtOAc and H2O
customThe organics were separated
extractionthe aqueous layer extracted with EtOAc (3×50 mL)
washThe combined organic extracts were washed with brine
dry with materialdried (MgSO4)
filtrationfiltered
concentrationconcentrated in vacuo

Sources & evidence

ORD record: ord-5c169e95ef9d44dcb933c0b56e040114
Source dataset: uspto-grants-2016_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09314456B2

Linked notes

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