Dichloromethane → HCID 15406052, compound

HRID 1457509Notes

Reaction equation

HRID 1457509 reaction equation
ClCCl.[C:4]([NH:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][C:29](O)=[O:30])([C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)([C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1.C(OC(Cl)=O)C(C)C.[C:40](#[N:44])[CH2:41][C:42]#[N:43]>C(N(CC)CC)C>[C:4]([NH:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][C:29](=[C:41]([C:40]#[N:44])[C:42]#[N:43])[OH:30])([C:11]1[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=1)([C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)[C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1

Participants

6

Reactant 4

HCID 6344DichloromethaneHCID 8010MalononitrileHCID 62365Isobutyl chloroformateHCID 5969746-(tritylamino)caproic acid

Product 1

HCID 15406052HCID 15406052, compoundYield 87.3%

Reagents, catalysts & solvents 1

HCID 8471TriethylamineSolvent

Procedure

To a dichloromethane solution of 6-(tritylamino)caproic acid (20.0 g, 53 mmole) and triethylamine (20 mL) in an ice bath was added dropwise over 30 min isobutylchloroformate (8.3 mL, 64 mmole). After the mixture was stirred for 2 hours in an ice bath, freshly distilled malononitrile (4.2 g, 64 mmole) was added all at once. The solution was stirred for 2 hours in an ice bath and for 2 hours at RT. The dichloromethane solution was washed with ice cold 2N HCl (300 mL) and the biphasic mixture was filtered to remove product that precipitated (13.2 g). The phases were separated and the organic layer dried and evaporated to a thick syrup. The syrup was covered with dichloromethane and on standing deposited fine crystals of product. The crystals were filtered and dried to give 6.3 g for a total yield of 19.5 g (87%) of the product, which is useful as an intermediate.

Workup

  1. stirringThe solution was stirred for 2 hours in an ice bath and for 2 hours at RT
  2. washThe dichloromethane solution was washed with ice cold 2N HCl (300 mL)
  3. filtrationthe biphasic mixture was filtered
  4. customto remove product that
  5. customprecipitated (13.2 g)
  6. customThe phases were separated
  7. customthe organic layer dried
  8. customevaporated to a thick syrup
  9. filtrationThe crystals were filtered
  10. customdried

Sources & evidence

ORD record
ord-368d8115966549b6b52f4dde965a59f7
Source dataset
uspto-grants-1998_12
Patent number
US05849482

Reaction notes

Loading…