3,3-Dimethyl-1-butyne → 2-Amino-3-(3,3-dimethylbut-1-ynyl)-5-nitrobenzonitrile

HRID 1991716Notes

Reaction equation

HRID 1991716 reaction equation
[NH2:1][C:2]1[C:9](Br)=[CH:8][C:7]([N+:11]([O-:13])=[O:12])=[CH:6][C:3]=1[C:4]#[N:5].[CH3:14][C:15]([CH3:19])([CH3:18])[C:16]#[CH:17]>CCN(CC)CC.[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[NH2:1][C:2]1[C:9]([C:17]#[C:16][C:15]([CH3:19])([CH3:18])[CH3:14])=[CH:8][C:7]([N+:11]([O-:13])=[O:12])=[CH:6][C:3]=1[C:4]#[N:5]

Participants

6

Reactant 2

HCID 135123,3-Dimethyl-1-butyneHCID 871732-Amino-3-bromo-5-nitrobenzonitrile

Product 1

HCID 591292522-Amino-3-(3,3-dimethylbut-1-ynyl)-5-nitrobenzonitrileYield 71%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent

Conditions

Temperature
80 °C

Procedure

To a stirred solution of 2-amino-3-bromo-5-nitrobenzonitrile (2.4 g, 10 mmol) in dry Et3N (60 mL) was added CuI (380 mg, 5% mol) and Pd(PPh3)2Cl2 (470 mg, 5% mol) at room temperature. 3,3-dimethyl-but-1-yne (2.1 g, 25 mmol) was added dropwise to the mixture at room temperature. The reaction mixture was stirred at 80° C. for 10 h. The reaction mixture was filtered and the filtrate was poured into ice (60 g), extracted with ethyl acetate. The phases were separated and the organic phase was dried over Na2SO4. The solvent was removed under vacuum to obtain the crude product, which was purified by column chromatography (2-10% EtOAc in petroleum ether) to obtain 2-amino-3-(3,3-dimethylbut-1-ynyl)-5-nitrobenzonitrile (1.7 g, 71%). 1H NMR (300 MHz, CDCl3) δ 8.28 (d, J=2.7 Hz, 1H), 8.27 (d, J=2.7 Hz, 1H), 5.56 (br s, 2H), 1.37 (s, 9H).

Workup

  1. filtrationThe reaction mixture was filtered
  2. additionthe filtrate was poured into ice (60 g)
  3. extractionextracted with ethyl acetate
  4. customThe phases were separated
  5. dry with materialthe organic phase was dried over Na2SO4
  6. customThe solvent was removed under vacuum
  7. customto obtain the crude product, which
  8. customwas purified by column chromatography (2-10% EtOAc in petroleum ether)

Sources & evidence

ORD record
ord-e517fbea52f84b50860e68fbd109fa81
Source dataset
uspto-grants-2010_01
Patent number
US07645789B2

Reaction notes

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