Acetonitrile → HCID 16090423, compound

HRID 2381566Notes

Reaction equation

HRID 2381566 reaction equation
CC#N.[CH3:4][O:5][C:6](=[O:22])[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=1[C:13](=[O:21])[C:14]1[CH:19]=[CH:18][C:17]([OH:20])=[CH:16][CH:15]=1.C(=O)([O-])[O-].[Cs+].[Cs+].[CH3:29][Si:30]([CH2:33][CH2:34][O:35][CH2:36]Cl)([CH3:32])[CH3:31]>C(OCC)(=O)C>[CH3:4][O:5][C:6](=[O:22])[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=1[C:13](=[O:21])[C:14]1[CH:15]=[CH:16][C:17]([O:20][CH2:36][O:35][CH2:34][CH2:33][Si:30]([CH3:32])([CH3:31])[CH3:29])=[CH:18][CH:19]=1

Participants

6

Reactant 4

HCID 6342AcetonitrileHCID 10796Cesium carbonateHCID 578713HCID 578713, compoundHCID 27242712-Chloromethyl 2-(trimethylsilyl)ethyl ether

Product 1

HCID 16090423HCID 16090423, compoundYield 68%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

Dry CH3CN (50 mL) was added to 2-(4-hydroxybenzoyl)benzoic acid methyl ester (3.65 g, 15 mmol) followed by cesium carbonate (5.4 g, 16.5 mmol) and trimethylsilylethoxymethylchloride (2.9 mL, 16.5 mmol). The system was stirred at room temperature under nitrogen for 24 h and monitored by TLC. Removal of the solvent gave a light yellow oil that was taken up into ethyl acetate (100 mL), washed with water (3×50 mL), brine (40 mL) and dried with MgSO4. The solvent was removed and the crude product was purified by flash column chromatography (5:95 EtOAc:petrol) to give 2-[4-(2-trimethylsilanylethoxymethoxy)benzoyl]benzoic acid methyl ester as a yellow oil (3.94 g, 10.2 mmol, 67%); Rf 0.79 (40:60 EtOAc:petrol). λmax (CH3OH)/nm 282, Abs 1.072. IR: 2939, 1720, 1666, 1589, 1489 cm−1. 1H NMR: (300 MHz, CDCl3) δ 0.00 (s, 9H, Si—(CH3)3), 0.94 (m, 2H, R—O—CH2—CH2—Si), 3.66 (s, 3H, COOCH3), 3.75 (m, 2H, O—CH2—CH2—Si), 5.27 (s, 2H, O—CH2—O), 7.05 (m, 2H, Ar—H), 7.37 (m, 1H, Ar—H), 7.53-7.66 (dtd, 2H, J=22.6, 7.4, 1.4 Hz, Ar—H), 7.72 (m, 2H, Ar—H), 8.05 (m, 1H, Ar—H). 13C NMR: (75 MHz, d6-DMSO) δ −2, 16.8, 51.5, 65.3, 91.5, 115.1, 127, 128, 129, 129.2, 129.6, 130.4, 132, 140.7, 160.2, 165.2, 194. LC/MS-ES+ m/z 163.2, 297.1, 387.1 [MH+], 409 [MNa+]. HRMS (EI) m/z Calcd. for C21H26O5Si: 386.1549. Found 386.1562.

Workup

  1. customRemoval of the solvent
  2. customgave a light yellow oil that
  3. washwashed with water (3×50 mL), brine (40 mL)
  4. dry with materialdried with MgSO4
  5. customThe solvent was removed
  6. customthe crude product was purified by flash column chromatography (5:95 EtOAc:petrol)

Sources & evidence

ORD record
ord-b82a0d0b95fd4a23ad7d0960fba95bf9
Source dataset
uspto-grants-2012_09
Patent number
US08258175B2

Reaction notes

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