Cesium carbonate → HCID 86667301, compound

HRID 2406987Notes

Reaction equation

[CH3:1][O:2][C:3]([C:5]1[N:10]=[CH:9][C:8](Br)=[CH:7][N:6]=1)=[O:4].C1C=CC(P(C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C([O-])([O-])=O.[Cs+].[Cs+].[C:64](=[NH:77])([C:71]1[CH:76]=[CH:75][CH:74]=[CH:73][CH:72]=1)[C:65]1[CH:70]=[CH:69][CH:68]=[CH:67][CH:66]=1>CC([O-])=O.CC([O-])=O.[Pd+2].C1(C)C=CC=CC=1>[CH3:1][O:2][C:3]([C:5]1[N:10]=[CH:9][C:8]([N:77]=[C:64]([C:65]2[CH:70]=[CH:69][CH:68]=[CH:67][CH:66]=2)[C:71]2[CH:76]=[CH:75][CH:74]=[CH:73][CH:72]=2)=[CH:7][N:6]=1)=[O:4]

Participants

Conditions

Temperature: 105 °C

Procedure

To a round bottom was added 5-bromo-pyrimidine-2-carboxylic acid methyl ester (14.50 g, 66.81 mmol), (+/−)-BINAP (4.16 g, 6.68 mmol), Pd(OAc)2 (750 mg, 3.34 mmol), and Cs2CO3 (26.1 g, 80.2 mmol). Toluene (100 mL) and benzophenone imine (12.3 mL, 73.5 mmol) were added and the mixture heated to 105° C. as an orange mixture. At 17 h, the reaction was cooled and partitioned between ethyl acetate and 1N NaOH. The aqueous layer was extracted with ethyl acetate and the combined organics dried over MgSO4. Purification by silica gel flash chromatography (ethyl acetate/heptane) gave 5-(benzhydrylidene-amino)-pyrimidine-2-carboxylic acid methyl ester (9.83 g, 46%) as a bright yellow solid. 1H NMR (400 MHz, DMSO-d6, δ): 8.42 (s, 2 H) 7.74 (d, J=6.8 Hz, 2 H) 7.61 (m, 1 H) 7.54 (m, 2 H) 7.38 (br. s., 3 H) 7.26 (br. s., 2 H) 3.83 (s, 3 H); MS (M+1): 318.2.

Workup

temperaturethe reaction was cooled
custompartitioned between ethyl acetate and 1N NaOH
extractionThe aqueous layer was extracted with ethyl acetate
dry with materialthe combined organics dried over MgSO4
customPurification by silica gel flash chromatography (ethyl acetate/heptane)

Sources & evidence

ORD record: ord-e52b42a248914c02a17f9becf5d76d76
Source dataset: uspto-grants-2014_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08809342B2

Reaction notes

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