Sodium → HCID 21467991, compound

HRID 54280Notes

Reaction equation

HRID 54280 reaction equation
[Na].[NH2:2][C:3]1[N:8]=[C:7]([NH2:9])[C:6](I)=[C:5]([CH3:11])[N:4]=1.[CH3:12][C:13]([C:20]1[CH:25]=[CH:24][C:23]([C:26]([F:29])([F:28])[F:27])=[CH:22][CH:21]=1)([CH3:19])/[CH:14]=[CH:15]/B(O)O>C(O)C>[NH2:2][C:3]1[N:8]=[C:7]([NH2:9])[C:6](/[CH:15]=[CH:14]/[C:13]([C:20]2[CH:21]=[CH:22][C:23]([C:26]([F:27])([F:29])[F:28])=[CH:24][CH:25]=2)([CH3:12])[CH3:19])=[C:5]([CH3:11])[N:4]=1

Participants

5

Reactant 3

HCID 5360545SodiumHCID 158557925-Iodo-6-methylpyrimidine-2,4-diamineHCID 21468004trans-3-Methyl-3-(4-trifluoromethylphenyl)-1-butenylboronic acid

Product 1

HCID 21467991HCID 21467991, compoundYield 56.5%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
80 °C

Procedure

Sodium metal, 4.1 grams (0.18 mole), was stirred with 250 mL of ethanol for 30 minutes. After this time 20.0 grams (0.08 mole) of 2,4-diamino-5-iodo-6-methylpyrimidine (prepared in Step B of Example 3), 27.6 grams (0.11 mole) of trans-3-methyl-3-(4-trifluoromethylphenyl)-1-butenylboronic acid, and 9.2 grams (0.008 mole) of tetrakistriphenylphosphine palladium(0) were added. The reaction mixture was purged with nitrogen, and then heated to 80° C. where it stirred for about 28 hours. After this time the reaction mixture was concentrated under reduced pressure to about 20% of the original volume and then poured into 300 mL of water. The mixture was cooled in an ice-bath, and a solid was collected by filtration. The solid was triturated with a mixture of 1:1 petroleum ether:diethyl ether, and then subjected to column chromatography on silica gel using 5% methanol in methylene chloride as the eluant. The product-containing fractions were combined and concentrated under reduced pressure to a solid residue. The solid was recrystallized from 1-propanol and water, yielding 15.2 grams of trans-2,4-diamino-6-methyl-5-[3-(4-trifluoromethylphenyl)-3-methyl-1-butenyl]pyrimidine, mp 182°-185° C. The NMR spectrum was consistent with the proposed structure.

Workup

  1. customThe reaction mixture was purged with nitrogen
  2. concentrationAfter this time the reaction mixture was concentrated under reduced pressure to about 20% of the original volume
  3. additionpoured into 300 mL of water
  4. temperatureThe mixture was cooled in an ice-bath
  5. filtrationa solid was collected by filtration
  6. customThe solid was triturated with a mixture of 1:1 petroleum ether
  7. concentrationconcentrated under reduced pressure to a solid residue
  8. customThe solid was recrystallized from 1-propanol and water

Sources & evidence

ORD record
ord-70aa6cbdaa024f8fb5516b67c593101f
Source dataset
uspto-grants-1997_04
Patent number
US05622954

Reaction notes

Loading…