Dicyclohexylcarbodiimide → 9-Chloro-4-methyl-3,4,5,6-tetrahydro-1H-benzo[e][1,4]diazocin-2-one

HRID 1743873Notes

Reaction equation

HRID 1743873 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][CH2:9][N:10]([CH2:12][C:13](O)=[O:14])[CH3:11])=[C:4]([N+:16]([O-])=O)[CH:3]=1.[H][H].C1(N=C=NC2CCCCC2)CCCCC1>CO.[Pt]>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]2[CH2:8][CH2:9][N:10]([CH3:11])[CH2:12][C:13](=[O:14])[NH:16][C:4]=2[CH:3]=1

Participants

6

Reactant 3

HCID 10868DicyclohexylcarbodiimideHCID 22236587{[2-(4-chloro-2-nitro-phenyl)-ethyl]-methyl-amino}-acetic AcidHCID 178418361HCID 178418361, compound

Product 1

HCID 222365829-Chloro-4-methyl-3,4,5,6-tetrahydro-1H-benzo[e][1,4]diazocin-2-one

Reagents, catalysts & solvents 2

HCID 23939PlatinumCatalystHCID 887MethanolSolvent

Conditions

Temperature
0 °C

Procedure

{[2-(4-Chloro-2-nitro-phenyl)-ethyl]-methyl-amino}-acetic acid (18.5 g, approximately 0.068 mole, not quite pure) in methanol (250 mL) containing platinum on sulfided carbon (5 wt. %, 12.0 g) was hydrogenated at room temperature and a hydrogen pressure of 50 psi overnight. The catalyst was removed by filtration through Celite and the filtrate was evaporated to dryness in vacuo. The residue was dissolved in pyridine (2 L) and the solution was cooled to 0° C., and 1,3-dicyclohexylcarbodiimide (30.0 g, 0.145 mol) was added. The reaction mixture was allowed to warm up to room temperature and stirred at room temperature for 48 hours. The solvent was removed and the residue was slurried with 10% hydrochloric acid and filtered. The filtrate was extracted with ether, the aqueous phase was made basic with sodium carbonate and then extracted with dichloromethane. The extract was dried over sodium sulfate and evaporated in vacuo. Purification by flash column chromatography (silica gel, methylene chloride) provided 5.1 g of the title compound as a white solid. 1H NMR (CDCl3): 7.55 δ (broad s, 1H); 7.18 δ (d, 1H); 7.10 δ (d, 1H); 7.00 δ (s, 1H); 3.18 δ (s, 2H); 2.80 δ (broad s, 4H); 2.40 δ (s, 3H).

Workup

  1. customwas hydrogenated at room temperature
  2. customThe catalyst was removed by filtration through Celite
  3. customthe filtrate was evaporated to dryness in vacuo
  4. dissolutionThe residue was dissolved in pyridine (2 L)
  5. temperatureto warm up to room temperature
  6. customThe solvent was removed
  7. filtrationfiltered
  8. extractionThe filtrate was extracted with ether
  9. extractionextracted with dichloromethane
  10. dry with materialThe extract was dried over sodium sulfate
  11. customevaporated in vacuo
  12. customPurification by flash column chromatography (silica gel, methylene chloride)

Sources & evidence

ORD record
ord-9e0ca2436fba4c858c79bd96daf8a241
Source dataset
uspto-grants-2006_03
Patent number
US07012089B2

Reaction notes

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