2-Methyl-6-nitro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline → 3-Methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene-1,2-diamine

HRID 1047209Notes

Reaction equation

HRID 1047209 reaction equation
[CH3:1][C:2]1[CH:8]=[C:7]([B:9]2[O:13][C:12]([CH3:15])([CH3:14])[C:11]([CH3:17])([CH3:16])[O:10]2)[CH:6]=[C:5]([N+:18]([O-])=O)[C:3]=1[NH2:4]>CO.[Pd]>[CH3:1][C:2]1[CH:8]=[C:7]([B:9]2[O:13][C:12]([CH3:15])([CH3:14])[C:11]([CH3:17])([CH3:16])[O:10]2)[CH:6]=[C:5]([NH2:18])[C:3]=1[NH2:4]

Participants

4

Reactant 1

HCID 251301272-Methyl-6-nitro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline

Product 1

HCID 666077053-Methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene-1,2-diamineYield 89%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Procedure

A solution of 2-Methyl-6-nitro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (5.3 g, 19.06 mmol) in methanol (50 mL) was purged with nitrogen gas. Palladium on carbon (10% by wt, 50 mg) was added and the reaction mixture was stirred under a hydrogen balloon for 16 h. The reaction was filtered through Celite and the filter cake was rinsed with methanol. The filtrate was concentrated and the resulting material was purified by silica gel column chromatography (0-100% ethyl acetate in hexanes) to give a dark oil. The oil was triturated with 10% ether in hexanes to give a tan colored solid (4.2 g, 16.9 mmol, 89% yield). MS (ESI) m/z 248.9 [M+1]+.

Workup

  1. filtrationThe reaction was filtered through Celite
  2. washthe filter cake was rinsed with methanol
  3. concentrationThe filtrate was concentrated
  4. customthe resulting material was purified by silica gel column chromatography (0-100% ethyl acetate in hexanes)
  5. customto give a dark oil
  6. customThe oil was triturated with 10% ether in hexanes

Sources & evidence

ORD record
ord-196dd7d857de4a9a89993c23873f6f06
Source dataset
uspto-grants-2013_10
Patent number
US08569494B2

Reaction notes

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