Water → 5-Oxo-5,6,7,8-tetrahydronaphthalene-1-carbonitrile

HRID 1807569Notes

Reaction equation

HRID 1807569 reaction equation
Br[C:2]1[CH:11]=[CH:10][CH:9]=[C:8]2[C:3]=1[CH2:4][CH2:5][CH2:6][C:7]2=[O:12].O.[CH3:14][N:15]1C(=O)CCC1>[C-]#N.[C-]#N.[Zn+2]>[O:12]=[C:7]1[CH2:6][CH2:5][CH2:4][C:3]2[C:2]([C:14]#[N:15])=[CH:11][CH:10]=[CH:9][C:8]1=2

Participants

5

Reactant 3

HCID 962WaterHCID 13387N-methyl-2-pyrrolidoneHCID 108895725-Bromo-1,2,3,4-tetrahydronaphthalen-1-one

Product 1

HCID 109318735-Oxo-5,6,7,8-tetrahydronaphthalene-1-carbonitrileYield 91%

Reagents, catalysts & solvents 1

HCID 11186Zinc cyanide (Zn(CN)2)Catalyst

Conditions

Temperature
110 °C

Procedure

To a stirred solution of 5-bromo-3,4-dihydronaphthalen-1(2H)-one (9.95 g, 44.2 mmol) in NMP (50 mL) was added Zn(CN)2 (10.38 g, 88.4 mmol). The mixture was degassed twice by bubbling N2 through the solution for 30 min then evacuated. Pd(Ph3)4 (0.5 g, 0.44 mmol) was added and the mixture was heated to 110° C. under N2. After 5 h, the mixture was cooled to room temperature and poured onto ice (600 mL), using water (300 mL) to complete the transfer. After the ice had melted, the solution was filtered and the resulting solid was collected, suspended in DCM, and filtered again. The solid was collected, washed with water, and purified by column chromatography (EA/hex) to provide 6.9 g (91%) of 5-oxo-5,6,7,8-tetrahydronaphthalene-1-carbonitrile INT-1 as a white solid. LCMS-ESI (m/z) calculated for C11H9NO: 171.2; found 172.1 [M+H]+, tR=2.95 min. 1H NMR (400 MHz, CDCl3) δ 8.26 (dd, J=7.9, 1.4 Hz, 1H), 7.82 (dd, J=7.6, 1.4 Hz, 1H), 7.44 (t, J=7.8 Hz, 1H), 3.20 (t, J=6.1 Hz, 2H), 2.72 (dd, J=7.2, 6.1 Hz, 2H), 2.30-2.17 (m, 2H). 13C NMR (101 MHz, CDCl3) δ 196.22, 147.39, 137.18, 133.39, 131.59, 127.19, 116.93, 112.94, 38.48, 28.05, 22.28.

Workup

  1. customThe mixture was degassed twice
  2. customby bubbling N2 through the solution for 30 min
  3. customthen evacuated
  4. temperaturethe mixture was cooled to room temperature
  5. additionpoured onto ice (600 mL)
  6. filtrationthe solution was filtered
  7. customthe resulting solid was collected
  8. filtrationfiltered again
  9. customThe solid was collected
  10. washwashed with water
  11. custompurified by column chromatography (EA/hex)

Sources & evidence

ORD record
ord-c0d13e2c430c46609315e8abbc75081d
Source dataset
uspto-grants-2013_01
Patent number
US08357706B2

Reaction notes

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