Dimethylformamide → 2-Chlorocyclohex-1-ene-1-carbonitrile

HRID 2276349Notes

Reaction equation

HRID 2276349 reaction equation
P(Cl)(Cl)(Cl)=O.C[N:7]([CH:9]=O)C.[C:11]1(=O)[CH2:16][CH2:15][CH2:14][CH2:13][CH2:12]1.[ClH:18].NO>>[Cl:18][C:11]1[CH2:16][CH2:15][CH2:14][CH2:13][C:12]=1[C:9]#[N:7]

Participants

5

Reactant 4

HCID 6228DimethylformamideHCID 7967CyclohexanoneHCID 24813Phosphorus oxychlorideHCID 443297Hydroxyamine hydrochloride

Product 1

HCID 498409392-Chlorocyclohex-1-ene-1-carbonitrileYield 83.1%

Conditions

Temperature
50 °C

Procedure

Phosphorus oxychloride (11.5 mL; 124 mmol) was cooled in an ice-salt bath and DMF (10.0 mL; 130 mmol) was added over a period of 20 min (a sticky white solid was formed). Cyclohexanone (8.0 mL; 77 mmol) was added over 15 min (the sticky solid turned into a bright yellow solution). The mixture was heated at 50° C. and hydroxylamine hydrochloride (30 g; 432 mmol) was added in 5 portions at 5 min intervals maintaining the temperature between 45 and 55° C. via cooling if needed. The reaction mixture was poured into ice-water (300 mL) and the aqueous mixture was stirred for 1 h. The brown solid was filtered, washed with water and dried under reduced pressure over phosphorus pentoxide to afford 9.06 g (83%) of 2-chlorocyclohex-1-enecarbonitrile as a rust-brown solid. ESI/APCI (+): 160-162 (M+H+H2O). 1H-NMR (400 MHz, DMSO-d6) (ppm) δ: 2.48 (2H, m); 2.35 (2H, m), 1.74-1.77 (2H, M), 1.71-1.66 (2H, M).

Workup

  1. customwas formed)
  2. temperaturemaintaining the temperature between 45 and 55° C.
  3. temperaturevia cooling
  4. filtrationThe brown solid was filtered
  5. washwashed with water
  6. dry with materialdried under reduced pressure over phosphorus pentoxide

Sources & evidence

ORD record
ord-583944477e56460193a43a30051d12de
Source dataset
uspto-grants-2015_09
Patent number
US09132129B2

Reaction notes

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