Carbon Tetrachloride → HCID 13959041, compound

HRID 255866Notes

Reaction equation

HRID 255866 reaction equation
[CH3:1][C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:11]=1[N:10]=[N:9][CH:8]=[C:7]2[C:12]([O:14][CH3:15])=[O:13].C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1.BrN1C(=O)CCC1=O.C(Cl)(Cl)(Cl)[Cl:43]>[W]>[Cl:43][CH2:1][C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:11]=1[N:10]=[N:9][CH:8]=[C:7]2[C:12]([O:14][CH3:15])=[O:13]

Participants

6

Reactant 4

HCID 5943Carbon TetrachlorideHCID 7187Benzoyl PeroxideHCID 67184N-bromobutanimideHCID 13959035HCID 13959035, compound

Product 1

HCID 13959041HCID 13959041, compound

Reagents, catalysts & solvents 1

HCID 23964TungstenCatalyst

Procedure

To 4.3 g of 50 in 1900 ml of carbon tetrachloride a few milligrams of benzoyl peroxide was added, followed by 3.2 g of N-bromosuccinimide and the stirred mixture was refluxed and irradiated with a 200-watt tungsten lamp for 6 hours. The resulting mixture was cooled, washed with water, then with very dilute aqueous sodium bicarbonate solution, dried (MgSO4) and stripped of solvent. The residue (methyl 8-(bromomethyl)cinnoline-4-carboxylate) (58A) was dissolved in 80 ml of acetone, 2.11 g of lithium chloride was added, and the mixture was stirred at room temperature over a weekend. The mixture was stripped of solvent and the residue was dissolved in methylene chloride. The solution was washed with water, dried (MgSO4) and stripped of solvent. The residue was flash chromatographed over silica gel, first using methylene chloride as eluent, then a 1:99 v:v mixture of ethyl acetate and methylene chloride as eluent, to give methyl 8-(chloromethyl)cinnoline-4-carboxylate (58B), as a solid, m.p.: 111°-112° C. (with decomposition).

Workup

  1. temperaturethe stirred mixture was refluxed
  2. temperatureThe resulting mixture was cooled
  3. washwashed with water
  4. dry with materialwith very dilute aqueous sodium bicarbonate solution, dried (MgSO4)
  5. dissolutionThe residue (methyl 8-(bromomethyl)cinnoline-4-carboxylate) (58A) was dissolved in 80 ml of acetone
  6. addition2.11 g of lithium chloride was added
  7. dissolutionthe residue was dissolved in methylene chloride
  8. washThe solution was washed with water
  9. dry with materialdried (MgSO4)
  10. customchromatographed over silica gel, first using methylene chloride as eluent
  11. additiona 1:99 v:v mixture of ethyl acetate and methylene chloride as eluent

Sources & evidence

ORD record
ord-e76e51b02fb74a629660f35b421d6976
Source dataset
uspto-grants-1987_10
Patent number
US04699651

Reaction notes

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