Dimethylformamide → HCID 13914704, compound

HRID 652609Notes

Reaction equation

HRID 652609 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[N:6]([CH2:27][CH2:28][NH:29][CH2:30][CH2:31][OH:32])[N:7]=[C:8]3[C:17]4[C:12](=[C:13]([O:18][CH2:19][C:20]5[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=5)[CH:14]=[CH:15][CH:16]=4)[C:11](=[O:26])[C:10]=1[C:9]=23.Br[CH2:34][C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1.C(=O)(O)[O-].[K+].CN(C)C=O>O>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[N:6]([CH2:27][CH2:28][N:29]([CH2:30][CH2:31][OH:32])[CH2:34][C:35]3[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=3)[N:7]=[C:8]3[C:17]4[C:12](=[C:13]([O:18][CH2:19][C:20]5[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=5)[CH:14]=[CH:15][CH:16]=4)[C:11](=[O:26])[C:10]=1[C:9]=23

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 7498Benzyl BromideHCID 516893Potassium BicarbonateHCID 13558464HCID 13558464, compound

Product 1

HCID 13914704HCID 13914704, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

A mixture of 14.5 g (32.3 mmol) of 5-chloro-2-[2-[(2-hydroxyethyl)]amino]-7-(phenylmethoxy)anthra[1,9-cd]pyrazol-6(2H)-one (5) and its 10-phenylmethoxy isomer (4), ~4:1 respectively by HPLC, 3.9 ml of α-bromotoluene, 6.5 g of potassium bicarbonate, and 140 ml of N,N-dimethylformamide was stirred at room temperature for 18 hr. The mixture was diluted with 500 ml of water and extracted with three 200 ml portions of dichloromethane. The combined organic extracts were washed with water, dried, and concentrated to an oil which was purified by chromatography on 600 g of silica gel (230-400 mesh). Elution with ethyl acetate:hexane (3:2) followed by concentration of product fractions gave the faster eluting component as a solid. Crystallization from acetonitrile afforded 3.55 g of pure isomer 9, mp 130°-134° C. Elution with ethyl acetate followed by concentration of product fractions afforded 9.2 g (66%) of slower eluting isomer 8 as a syrup which could not be crystallized.

Workup

  1. extractionextracted with three 200 ml portions of dichloromethane
  2. washThe combined organic extracts were washed with water
  3. customdried
  4. concentrationconcentrated to an oil which
  5. customwas purified by chromatography on 600 g of silica gel (230-400 mesh)
  6. washElution with ethyl acetate:hexane (3:2)
  7. customgave the
  8. washfaster eluting component as a solid
  9. customCrystallization from acetonitrile
  10. customafforded 3.55 g of pure isomer 9, mp 130°-134° C
  11. washElution with ethyl acetate
  12. customafforded 9.2 g (66%)
  13. washof slower eluting isomer 8 as a syrup which could not
  14. custombe crystallized

Sources & evidence

ORD record
ord-c2f3002fd9084668806fd50878421f63
Source dataset
uspto-grants-1987_06
Patent number
US04672129

Reaction notes

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