Sodium Carbonate → 2-(Methylthio)-4-(2-(4-nitrophenoxy)phenyl)pyrimidine

HRID 446286Notes

Reaction equation

HRID 446286 reaction equation
CC1(C)C(C)(C)OB([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=2[O:15][C:16]2[CH:21]=[CH:20][C:19]([N+:22]([O-:24])=[O:23])=[CH:18][CH:17]=2)O1.C(=O)([O-])[O-].[Na+].[Na+].Cl[C:33]1[CH:38]=[CH:37][N:36]=[C:35]([S:39][CH3:40])[N:34]=1>O1CCOCC1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH3:40][S:39][C:35]1[N:36]=[C:37]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=2[O:15][C:16]2[CH:17]=[CH:18][C:19]([N+:22]([O-:24])=[O:23])=[CH:20][CH:21]=2)[CH:38]=[CH:33][N:34]=1

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 971134-Chloro-2-methylthiopyrimidineHCID 667316814,4,5,5-Tetramethyl-2-(2-(4-nitrophenoxy)phenyl)-1,3,2-dioxaborolane

Product 1

HCID 669704222-(Methylthio)-4-(2-(4-nitrophenoxy)phenyl)pyrimidine

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 312751,4-DioxaneSolvent

Procedure

To a mixture of 4,4,5,5-tetramethyl-2-(2-(4-nitrophenoxy)phenyl)-1,3,2-dioxaborolane (0.936 g, 2.7 mmol), Pd(dppf)Cl2 (0.10 g, 0.14 mmol) in dioxane and Sodium carbonate (2.0 M in water, 2.7 ml, 5.5 mmol) was added 4-chloro-2-methylthiopyrimidine (0.38 ml, 3.3 mmol). The brown mixture was sealed and heated to 80 deg. C. overnight. In the morning the reaction was partitioned between EtOAc/1N NaOH. The aqueous layer was extracted once with EtOAc. The combined organics were dried over anhyd. Na2SO4, filtered, and concentrated to a brown oil. This material was treated with CH2Cl2 and purified by silica gel chromatography eluting with 0-25% EtOAc/hexane. The product-containing fractions were concentrated to afford 2-(methylthio)-4-(2-(4-nitrophenoxy)phenyl)pyrimidine as a clear oil. MS m/z=340 [M+1]+. Calc'd for C17H13N3O3: 339.37.

Workup

  1. customThe brown mixture was sealed
  2. temperatureheated to 80 deg. C
  3. customovernight
  4. customIn the morning the reaction was partitioned between EtOAc/1N NaOH
  5. extractionThe aqueous layer was extracted once with EtOAc
  6. customThe combined organics were dried over anhyd
  7. filtrationNa2SO4, filtered
  8. concentrationconcentrated to a brown oil
  9. additionThis material was treated with CH2Cl2
  10. custompurified by silica gel chromatography
  11. washeluting with 0-25% EtOAc/hexane
  12. concentrationThe product-containing fractions were concentrated

Sources & evidence

ORD record
ord-4f0f9fc55fb94288ba10b22fad34c127
Source dataset
uspto-grants-2013_07
Patent number
US08476434B2

Reaction notes

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