Dichloromethane → 5-Bromo-2-phenylpyrimidine

HRID 589168Notes

Reaction equation

HRID 589168 reaction equation
[Br:1][C:2]1[CH:3]=[N:4][C:5](I)=[N:6][CH:7]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].[C:17]1(B(O)O)[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1.C(Cl)Cl>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]>[Br:1][C:2]1[CH:3]=[N:4][C:5]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)=[N:6][CH:7]=1

Participants

7

Reactant 4

HCID 6344DichloromethaneHCID 62657Potassium Phosphate, TribasicHCID 66827Phenylboronic AcidHCID 70066515-Bromo-2-iodopyrimidine

Product 1

HCID 143877455-Bromo-2-phenylpyrimidineYield 86%

Reagents, catalysts & solvents 2

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

Conditions

Temperature
120 °C

Procedure

A mixture of 5-bromo-2-iodopyrimidine (285 mg, 1.0 mmol), potassium phosphate (637 mg, 3.0 mmol), phenylboronic acid (134 mg, 1.1 mmol) and dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium (II) dichloromethane adduct (73 mg, 0.1 mmol) in dioxane (5 mL) was heated to 120° C. for 20 minutes in a microwave. LC/MS analysis of the reaction indicated that the reaction was complete. DCM (10 mL) was added, and the precipitates removed by passing through a plug of celite. The filtrate was concentrated, and the crude residue purified by flash column chromatography, gradient elution (0 to 100%) hexane/ethyl acetate, to afford compound Int-1a as a white solid (201 mg, 86% yield). HPLC-MS tR=1.39 min (UV254 nm); mass calculated for formula C10H7BrN4 233.98, observed LCMS m/z 235.0 (M+H).

Workup

  1. customthe precipitates removed
  2. concentrationThe filtrate was concentrated
  3. customthe crude residue purified by flash column chromatography, gradient elution (0 to 100%) hexane/ethyl acetate

Sources & evidence

ORD record
ord-de57cd42f1db48cba39b215979161ae7
Source dataset
uspto-grants-2016_01
Patent number
US09227971B2

Reaction notes

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