p-Acetamidobenzoic acid → 4-Acetylamino-N-[2-nitro-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-benzamide

HRID 252828

Reaction equation

HRID 252828 reaction equation
[CH3:1][C:2]1([CH3:19])[C:6]([CH3:8])([CH3:7])[O:5][B:4]([C:9]2[CH:10]=[CH:11][C:12]([N+:16]([O-:18])=[O:17])=[C:13]([NH2:15])[CH:14]=2)[O:3]1.[C:20]([NH:23][C:24]1[CH:32]=[CH:31][C:27]([C:28](Cl)=[O:29])=[CH:26][CH:25]=1)(=[O:22])[CH3:21].C(NC1C=CC(C(O)=O)=CC=1)(=O)C>N1C=CC=CC=1.CN(C)C1C=CN=CC=1>[C:20]([NH:23][C:24]1[CH:32]=[CH:31][C:27]([C:28]([NH:15][C:13]2[CH:14]=[C:9]([B:4]3[O:3][C:2]([CH3:19])([CH3:1])[C:6]([CH3:7])([CH3:8])[O:5]3)[CH:10]=[CH:11][C:12]=2[N+:16]([O-:18])=[O:17])=[O:29])=[CH:26][CH:25]=1)(=[O:22])[CH3:21]

Participants

6

Reactant 3

HCID 19266p-Acetamidobenzoic acidHCID 70103414-Acetamidobenzoyl chlorideHCID 597369762-Nitro-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline

Product 1

HCID 597367494-Acetylamino-N-[2-nitro-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-benzamideYield 16%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 1049PyridineSolvent

Procedure

To a solution of compound 132 (18 mg, 0.689 mmol) in pyridine (2.8 mL) was added 4-acetamidobenzoyl chloride (150 mg, 0.758 mmol) and 4-(dimethylamino)pyridine (8 mg, 0.07 mmol) and the mixture was stirred for 16 h. at r.t. Then, it was partitioned between EtOAc and H2O, The aqueous layer was extracted with fresh EtOAc and the combined organic layers were washed with brine, dried over MgSO4, filtered and concentrated in vacuo. The resulting crude oil was purified by flash chromatography on silica gel using methanol/EtOAc (5:95) as the eluent affording the title compound 133 (47 mg, 16% yield) as a 1:1 mixture with 4-acetamidobenzoic acid (hydrolyzed starting material). 1H NMR: (Acetone-d6) δ(ppm): 10.76 (bs, 1H), 9.52 (bs, 1H), 9.00 (d, J=1.0 Hz, 1H), 8.20 (d, J=7.2 Hz, 1H), 7.99 (d, J=8.6 Hz, 2H), 7.85 (d, J=8.6 Hz, 2H), 7.64 (dd, J=8.2, 1.2 Hz, 1H), 2.15 (s, 3H), 1.40 (s, 12H).

Workup

  1. customThen, it was partitioned between EtOAc and H2O
  2. extractionThe aqueous layer was extracted with fresh EtOAc
  3. washthe combined organic layers were washed with brine
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe resulting crude oil was purified by flash chromatography on silica gel

Sources & evidence

ORD record
ord-f3ebc4f6d88642c18ad4ee41ff658ec1
Source dataset
uspto-grants-2011_01
Patent number
US07868205B2

Linked notes

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