Cesium carbonate → HCID 86667301, compound

HRID 2173848Notes

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 1 N 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, 2H) 7.74 (d, J=6.8 Hz, 2H) 7.61 (m, 1H) 7.54 (m, 2H) 7.38 (br. s., 3H) 7.26 (br. s., 2H) 3.83 (s, 3H); MS (M+1): 318.2.

Workup

temperaturethe reaction was cooled
custompartitioned between ethyl acetate and 1 N 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-6ac88c48d74f4cb49001c44a0645bfb9
Source dataset: uspto-grants-2015_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09056834B2

Reaction notes

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