Hexamethyldisilazane → 3-Isopropoxy-5-(4-phosphono-phenoxy)-benzoic acid 2-trimethylsilanyl-ethyl ester

HRID 1431031Notes

Reaction equation

HRID 1431031 reaction equation
[CH3:1][Si:2]([CH3:36])([CH3:35])[CH2:3][CH2:4][O:5][C:6](=[O:34])[C:7]1[CH:12]=[C:11]([O:13][CH:14]([CH3:16])[CH3:15])[CH:10]=[C:9]([O:17][C:18]2[CH:23]=[CH:22][C:21]([P:24]([O:30]C(C)C)([O:26]C(C)C)=[O:25])=[CH:20][CH:19]=2)[CH:8]=1.C[Si](N[Si](C)(C)C)(C)C.[Si](Br)(C)(C)C>C(Cl)Cl>[CH3:36][Si:2]([CH3:1])([CH3:35])[CH2:3][CH2:4][O:5][C:6](=[O:34])[C:7]1[CH:8]=[C:9]([O:17][C:18]2[CH:19]=[CH:20][C:21]([P:24]([OH:30])([OH:26])=[O:25])=[CH:22][CH:23]=2)[CH:10]=[C:11]([O:13][CH:14]([CH3:15])[CH3:16])[CH:12]=1

Participants

5

Reactant 3

HCID 13838HexamethyldisilazaneHCID 76113BromotrimethylsilaneHCID 585289823-[4-(Diisopropoxy-phosphoryl)-phenoxy]-5-isopropoxy-benzoic acid 2-trimethylsilanyl-ethyl ester

Product 1

HCID 585288333-Isopropoxy-5-(4-phosphono-phenoxy)-benzoic acid 2-trimethylsilanyl-ethyl esterYield 65.1%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of 3-[4-(diisopropoxy-phosphoryl)-phenoxy]-5-isopropoxy-benzoic acid 2-trimethylsilanyl-ethyl ester (5.0 g, 9.30 mmol) in CH2Cl2 (100 mL) was added HMDS (31.7 Ml, 149 mmol), and TMS-Br (9.8 mL, 74.5 mmol). The mixture was stirred at rt for 16 h. The solvent was evaporated and the residue was diluted with water and acidified to pH 2-3 with aqueous HCl. Extracted into EtOAc (2×). The extract was washed with dilute HCl, water, and brine. Dried (MgSO4) and evaporated to provide 2.74 g of 3-Isopropoxy-5-(4-phosphono-phenoxy)-benzoic acid 2-trimethylsilanyl-ethyl ester. 1H NMR (500 MHz, DMSO-d6): δ 7.71 (dd, J=13, 9 Hz, 2H), 7.22 (dd, J=3, 2 Hz, 1H), 7.11 (dd, J=9, 3 Hz, 2H), 7.03 (dd, J=3, 2 Hz, 1H), 6.92 (t, J=3 Hz, 1H), 4.67 (m, 1H), 4.34 (t, 2H), 1.27 (d, J=6 Hz, 6H), 1.05 (t, 2H), 0.01 (s, 9H).

Workup

  1. customThe solvent was evaporated
  2. additionthe residue was diluted with water
  3. extractionExtracted into EtOAc (2×)
  4. washThe extract was washed with dilute HCl, water, and brine
  5. dry with materialDried (MgSO4)
  6. customevaporated

Sources & evidence

ORD record
ord-a30b7e542a584c7a88656d299865e375
Source dataset
uspto-grants-2015_01
Patent number
US08940927B2

Reaction notes

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