Carbon tetrabromide → HCID 135730596, compound

HRID 354182Notes

Reaction equation

HRID 354182 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH2:20]([O:24][C:25]1[C:30]([C:31]2[NH:32][C:33](=[O:46])[C:34]3[C:35](=[C:37]([CH2:44][CH3:45])[N:38]([CH2:40][CH2:41][O:42][CH3:43])[N:39]=3)[N:36]=2)=[CH:29][C:28]([C:47](=[O:50])[CH2:48]O)=[CH:27][N:26]=1)[CH2:21][CH2:22][CH3:23].C(Br)(Br)(Br)[Br:52]>ClCCl>[CH2:20]([O:24][C:25]1[C:30]([C:31]2[NH:32][C:33](=[O:46])[C:34]3[C:35](=[C:37]([CH2:44][CH3:45])[N:38]([CH2:40][CH2:41][O:42][CH3:43])[N:39]=3)[N:36]=2)=[CH:29][C:28]([C:47](=[O:50])[CH2:48][Br:52])=[CH:27][N:26]=1)[CH2:21][CH2:22][CH3:23]

Participants

5

Reactant 3

HCID 11205Carbon tetrabromide2×HCID 11776Triphenylphosphine2×HCID 135730584HCID 135730584, compound

Product 1

HCID 135730596HCID 135730596, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

Triphenylphosphine (110 mg, 0.42 mmol) in dichloromethane (1 mL) was added slowly to an ice cooled solution of 5-(2-butoxy-5-glycoloyl-3-pyridinyl)-3-ethyl-2-(2-methoxyethyl)-2,6-dihydro-7H-pyrazolo[4,3-d]-pyrimidin-7-one (Example 33) (150 mg, 0.35 mmol) and carbon tetrabromide (140 mg, 0.42 mmol) in dichloromethane (3 mL). The solution was allowed to warm to room temperature. After 2 h further carbon tetrabromide (25 mg, 0.075 mmol) and triphenylphosphine were added and stirring continued for 2 h. Concentration and purification of the product by flash column chromatography (gradient elution with ethyl acetate/pentane (10:90-70:30) gave 5-[2-butoxy-5-(2-bromoacetyl)-3-pyridinyl]-3-ethyl-2-(2-methoxyethyl)-2,6-dihydro-7H-pyrazolo[4,3-d]-pyrimidin-7-one which was used without any further purification (slight contamination with triphenylphosphine oxide). 5-[2-Butoxy-5-(2-bromoacetyl)-3-pyridinyl]-3-ethyl-2-(2-methoxyethyl)-2,6-dihydro-7H-pyrazolo[4,3-d]pyrimidin-7-one (205 mg, 0.42 mmol) was dissolved in dichloromethane and the solution cooled to 0° C. Morpholine (54 mg, 0.62 mmol) and triethylamine (84 mg, 0.83 mmol) were added and the mixture was allowed to warm to room temperature and stirred for 2 h. The solvent was evaporated and the residue dissolved in ethyl acetate, washed with water (twice), saturated sodium bicarbonate (twice) and brine, dried (MgSO4) and concentrated. Purification by flash column chromatography (gradient elution 20% ethyl acetate/pentane:100% ethyl acetate:3% methanol/methyl acetate) gave 70 mg product.

Workup

  1. concentrationConcentration and purification of the product by flash column chromatography (
  2. washgradient elution with ethyl acetate/pentane (10:90-70:30)

Sources & evidence

ORD record
ord-15fa678a023a4d79a5869e9d7fad7a0e
Source dataset
uspto-grants-2004_06
Patent number
US06756373B1

Reaction notes

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