Hydrochloric Acid → 3-Chlorospiro-[5,6,7,8-tetrahydroquinolin-5,4'-imidazolidine]-2',5'-dione

HRID 1591254Notes

Reaction equation

HRID 1591254 reaction equation
Cl[C:2]1[CH:3]=N[C:5]2[CH2:6][CH2:7][CH2:8][C:9](=O)[C:10]=2[CH:11]=1.S(=O)(O)[O-:14].[Na+].[C:18](=O)([O-])[O-:19].[NH4+:22].[NH4+:23].[C-:24]#[N:25].[K+].[ClH:27]>C(N)=O.O>[Cl:27][C:2]1[CH:3]=[N:22][C:5]2[CH2:6][CH2:7][CH2:8][C:9]3([C:10]=2[CH:11]=1)[C:18](=[O:19])[NH:25][C:24](=[O:14])[NH:23]3

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 9032Potassium CyanideHCID 517111Ammonium CarbonateHCID 109976543-Chloro-7,8-dihydroquinolin-5(6H)-oneHCID 23665763Sodium Bisulfite

Product 1

HCID 109995133-Chlorospiro-[5,6,7,8-tetrahydroquinolin-5,4'-imidazolidine]-2',5'-dione

Reagents, catalysts & solvents 2

HCID 713FormamideSolventHCID 962WaterSolvent2×

Procedure

3-Chloro-5,6,7,8-tetrahydroquinolin-5-one (125 grams, 0.689 mol) was suspended in formamide (98%, 1 L) with sodium bisulfite (73 grams, 0.7 mol). The mixture was mechanically stirred while ammonium carbonate (285 grams, 2.97 mol) was added in portions. This caused some foaming which limited the rate of addition. After the initial foaming subsided, potassium cyanide (90 grams, 1.38 mol) was added in one portion as a solid. The reaction mixture was stirred at room temperature for 3 days. The reaction was diluted with water (500 ml) and cooled in an ice water bath. The reaction pH was 9.91. 6N HCl (about 550 ml) was added dropwise to give a stable pH of 7.2. Again there was some foaming toward the end of the pH adjustment and the gases were scrubbed with a caustic trap. Water (500 ml) was added to further dilute the reaction and the mixture was granulated for 1/2 hour. The product was filtered and air dried overnight. The crude solid was broken up and slurried in acetonitrile (600 ml) for 45 minutes. The solid product was filtered, washed with acetonitrile and dried in vacuo at 40° C. Yield 134 grams (77.5%); mp 230°-3° C. NMR (DMSO, d6, 300 MHz) δ10.7 (bs, 1), 8.6 (s, 1), 8.5 (d, 1), 7.65 (d, 1), 2.9 (t, 2), 2.15 (m, 2), 1.9 (m, 2).

Workup

  1. additionwas added in portions
  2. additionthe rate of addition
  3. temperaturecooled in an ice water bath
  4. customThe reaction pH was 9.91
  5. customto give a stable pH of 7.2
  6. customthe gases were scrubbed with a caustic trap
  7. additionto further dilute
  8. customthe reaction
  9. waitthe mixture was granulated for 1/2 hour
  10. filtrationThe product was filtered
  11. customair dried overnight
  12. waitslurried in acetonitrile (600 ml) for 45 minutes
  13. filtrationThe solid product was filtered
  14. washwashed with acetonitrile
  15. customdried in vacuo at 40° C

Sources & evidence

ORD record
ord-b754cf765eba4f508575b8227af931ed
Source dataset
uspto-grants-1993_04
Patent number
US05206367

Reaction notes

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