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

HRID 1964301Notes

Reaction equation

HRID 1964301 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, 1 H), 8.27 (d, J=2.7 Hz, 1 H), 5.56 (br s, 2 H), 1.37 (s, 9 H).

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-fc18bf2d3ea949c4bc7e6fd145b5ff0e
Source dataset
uspto-grants-2013_04
Patent number
US08415387B2

Reaction notes

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