Dimethylformamide → HCID 22313315, compound

HRID 965829Notes

Reaction equation

HRID 965829 reaction equation
[CH2:1]([CH:3]1[O:8][C:7]2[CH:9]=[C:10](I)[CH:11]=[CH:12][C:6]=2[O:5][CH2:4]1)[CH3:2].[CH3:14][N:15](C=O)C>[C-]#N.[C-]#N.[Zn+2].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:1]([CH:3]1[CH2:4][O:5][C:6]2[CH:12]=[CH:11][C:10]([C:14]#[N:15])=[CH:9][C:7]=2[O:8]1)[CH3:2]

Participants

5

Reactant 2

HCID 6228DimethylformamideHCID 22313325HCID 22313325, compound

Product 1

HCID 22313315HCID 22313315, compoundYield 92%

Reagents, catalysts & solvents 2

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 178418397HCID 178418397, compoundCatalyst

Conditions

Temperature
80 °C

Procedure

A solution of 2-ethyl-7-iodo-2,3-dihydro-1,4-benzodioxine (486 mg, 1.68 mmol) in DMF (3 mL) is degassed by repeatedly evacuating the flask and filling with N2. Zn(CN)2 (117 mg, 1.0 mmol), and Pd(PPh3)4 (97 mg, 0.084 mmol) are added, and the resulting solution is degassed, and is then heated to 80° C. for 1.5 h. The reaction is allowed to cool, poured into water and extracted two times with ether. The combined organic extracts are dried (Na2SO4), filtered and concentrated in vacuo. The resulting material is purified by column chromatography (step gradient, 25-50% CH2Cl2 in hexanes) to give 3-ethyl-2,3-dihydro-1,4-benzodioxine-6-carbonitrile as a clear oil (296 mg, 92%). 1H NMR (400 MHz, CDCl3) δ 7.16, 7.13, 6.91, 4.31, 4.05, 3.93, 1.7, 1.6, 1.08.

Workup

  1. customby repeatedly evacuating the flask
  2. customthe resulting solution is degassed
  3. temperatureto cool
  4. additionpoured into water
  5. extractionextracted two times with ether
  6. dry with materialThe combined organic extracts are dried (Na2SO4)
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe resulting material is purified by column chromatography (step gradient, 25-50% CH2Cl2 in hexanes)

Sources & evidence

ORD record
ord-b2dbcdc884c5492193381d5e9cb335ce
Source dataset
uspto-grants-2005_10
Patent number
US06951868B2

Reaction notes

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