Potassium Carbonate → 4-(2,4-Diaminopyrido[3,2-d]pyrimidin-6(5H)-ylidene)-2-methoxycyclohexa-2,5-dien-1-one

HRID 1517411Notes

Reaction equation

HRID 1517411 reaction equation
[NH2:1][C:2]1[N:3]=[C:4]([NH2:13])[C:5]2[N:11]=[C:10](Cl)[CH:9]=[CH:8][C:6]=2[N:7]=1.C([O-])([O-])=O.[K+].[K+].[CH3:20][O:21][C:22]1[CH:27]=[C:26](B2OC(C)(C)C(C)(C)O2)[CH:25]=[CH:24][C:23]=1[OH:37]>O1CCOCC1.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[NH2:1][C:2]1[N:3]=[C:4]([NH2:13])[C:5]2[N:11]=[C:10]([C:26]3[CH:25]=[CH:24][C:23]([OH:37])=[C:22]([O:21][CH3:20])[CH:27]=3)[CH:9]=[CH:8][C:6]=2[N:7]=1

Participants

7

Reactant 3

HCID 11430Potassium CarbonateHCID 27346502-Methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenolHCID 133817146-Chloropyrido[3,2-d]pyrimidine-2,4-diamine

Product 1

HCID 1359032524-(2,4-Diaminopyrido[3,2-d]pyrimidin-6(5H)-ylidene)-2-methoxycyclohexa-2,5-dien-1-oneYield 69%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Procedure

A suspension of 2,4-diamino-6-chloropyrido[3,2-d]pyrimidine (378 mg, 1.93 mmole), K2CO3 (1075 mg, 7.78 mmole) and 2-methoxy-4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenol (599 mg, 2.32 mmole) in 1,4-dioxane (29 ml) and water (6 ml) was purged with a nitrogen stream for 30 minutes. Then, tetrakis(triphenylphosphine)palladium(0) (240 mg, 0.21 mmole) was added and purging with N2 was continued for 15 minutes. The reaction mixture was then heated at reflux under a N2 atmosphere for 2 hours. Upon cooling, the mixture was partitioned between CH2Cl2 and brine and the organic phase was dried over Na2SO4, filtered and evaporated under reduced pressure. Purification of the residue by silica gel flash chromatography with 10% methanol and 1% Et3N in CH2Cl2 as mobile phase, afforded the pure title compound (375 mg, yield 69%) which was characterized by its mass spectrum as follows: MS (m/z): 284 ([M+H]+, 100).

Workup

  1. customwas purged with a nitrogen stream for 30 minutes
  2. custompurging with N2
  3. temperatureThe reaction mixture was then heated
  4. temperatureat reflux under a N2 atmosphere for 2 hours
  5. temperatureUpon cooling
  6. customthe mixture was partitioned between CH2Cl2 and brine
  7. dry with materialthe organic phase was dried over Na2SO4
  8. filtrationfiltered
  9. customevaporated under reduced pressure
  10. customPurification of the residue by silica gel flash chromatography with 10% methanol and 1% Et3N in CH2Cl2 as mobile phase

Sources & evidence

ORD record
ord-a92f2e356f5a4fcdb074f19c143b9fcf
Source dataset
uspto-grants-2012_07
Patent number
US08232278B2

Reaction notes

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