Fumaric Acid → HCID 23045319, compound

HRID 2108140Notes

Reaction equation

HRID 2108140 reaction equation
[NH2:1][C:2]1[C:7]([Cl:8])=[CH:6][C:5]([CH:9]([CH2:11][N:12](CC2C=CC=CC=2)[CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][O:19][CH2:20][CH2:21][O:22][CH2:23][CH2:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][N:26]=2)[OH:10])=[CH:4][C:3]=1[Cl:38].Cl.C(O)C.[H][H].C(O)(=O)/C=C/C(O)=O>C(O)C.ClCCl.CO.[Pd]=O>[NH2:1][C:2]1[C:7]([Cl:8])=[CH:6][C:5]([CH:9]([CH2:11][NH:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][O:19][CH2:20][CH2:21][O:22][CH2:23][CH2:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][N:26]=2)[OH:10])=[CH:4][C:3]=1[Cl:38]

Participants

9

Reactant 4

HCID 444972Fumaric AcidHCID 21887872Ethanol hydrochlorideHCID 23045300HCID 23045300, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 23045319HCID 23045319, compoundYield 65%

Reagents, catalysts & solvents 4

HCID 5083724Palladium monoxideCatalystHCID 702EthanolSolvent2×HCID 887MethanolSolventHCID 6344DichloromethaneSolvent2×

Procedure

A solution of 4-amino-3,5-dichloro-α-[[(phenylmethyl)[6-[2-[2(2-pyridinyl)ethoxy]ethoxy]hexyl]amino]methyl]benzenemethanol (1.1 g,) in ethanol (25 ml) was hydrogenated over pre-reduced 10% palladium oxide on charcoal catalyst (50% aqueous paste, 600 mg) in ethanol (10 ml) containing 1:9 conc. hydrochloric acid/ethanol, (1.78 ml,) until the uptake of hydrogen ceased (1 h). The mixture was filtered and evaporated in vacuo to give an oil which was dissolved in dichloromethane (100 ml) and washed with 8% sodium bicarbonate (50 ml). The aqueous phase was re-extracted with dichloromethane (50 ml) and the combined organic phases dried and evaporated in vacuo to give an oil. Purification by FCC eluting with System G (95:5:1) gave a colourless oil, which was dissolved in methanol (10 ml) and treated with fumaric acid (0.09 g), evaporated in vacuo and triturated with diethyl ether to give a white solid (0.75 g,). The solid was dissolved in dichloromethane (150 ml) and washed with 8% sodium bicarbonate (100 ml). The aqueous layer was re-extracted with dichloromethane (100 ml) and the combined organic fractions dried and evaporated in vacuo to give an oil. Trituration with System F (ca. 10:1) gave the title compound (0.60 g,) as a white solid m.p. 45.5°-46.5°. T.l.c. (System E 40:10:1) Rf 0.49.

Workup

  1. custom(1 h)
  2. filtrationThe mixture was filtered
  3. customevaporated in vacuo
  4. customto give an oil which
  5. washwashed with 8% sodium bicarbonate (50 ml)
  6. extractionThe aqueous phase was re-extracted with dichloromethane (50 ml)
  7. customthe combined organic phases dried
  8. customevaporated in vacuo
  9. customto give an oil
  10. customPurification by FCC
  11. washeluting with System G (95:5:1)
  12. customgave a colourless oil, which
  13. customevaporated in vacuo
  14. customtriturated with diethyl ether
  15. customto give a white solid (0.75 g,)
  16. washwashed with 8% sodium bicarbonate (100 ml)
  17. extractionThe aqueous layer was re-extracted with dichloromethane (100 ml)
  18. customthe combined organic fractions dried
  19. customevaporated in vacuo
  20. customto give an oil

Sources & evidence

ORD record
ord-d60d373fa0fd401885fe5a1d443cb84b
Source dataset
uspto-grants-1990_06
Patent number
US04937268

Reaction notes

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