Diisopropylethylamine → Phosphorous acid mono-{4-[6-methoxy-7-methyl-3-oxo-4-(2-trimethylsilanyl-ethoxy)-1,3-dihydro-isobenzofuran-5-yl]-2-methyl-but-2-enyl} ester

HRID 272219

Reaction equation

HRID 272219 reaction equation
[OH:1][CH2:2][C:3]([CH3:26])=[CH:4][CH2:5][C:6]1[C:14]([O:15][CH2:16][CH2:17][Si:18]([CH3:21])([CH3:20])[CH3:19])=[C:13]2[C:9]([CH2:10][O:11][C:12]2=[O:22])=[C:8]([CH3:23])[C:7]=1[O:24][CH3:25].CCN(C(C)C)C(C)C.Cl[P:37]1[O:42]C(=O)C2C=CC=CC=2[O:38]1>O1CCOCC1>[CH3:25][O:24][C:7]1[C:8]([CH3:23])=[C:9]2[C:13]([C:12](=[O:22])[O:11][CH2:10]2)=[C:14]([O:15][CH2:16][CH2:17][Si:18]([CH3:20])([CH3:19])[CH3:21])[C:6]=1[CH2:5][CH:4]=[C:3]([CH3:26])[CH2:2][O:1][P:37]([OH:42])[OH:38]

Participants

5

Reactant 3

HCID 81531Diisopropylethylamine2×HCID 2370102-Chloro-4H-1,3,2-benzodioxaphosphorin-4-one2×HCID 670102606-(4-Hydroxy-3-methyl-but-2-enyl)-5-methoxy-4-methyl-7-(2-trimethylsilanyl-ethoxy)3H-isobenzofuran-1-one

Product 1

HCID 67010409Phosphorous acid mono-{4-[6-methoxy-7-methyl-3-oxo-4-(2-trimethylsilanyl-ethoxy)-1,3-dihydro-isobenzofuran-5-yl]-2-methyl-but-2-enyl} ester

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

To a solution of 6-(4-hydroxy-3-methyl-but-2-enyl)-5-methoxy-4-methyl-7-(2-trimethylsilanyl-ethoxy)-3H-isobenzofuran-1-one (75 mg, 0.20 mmol) and DIEA (49 μL, 0.28 mmol) in dioxane (2 mL) was added 2-chloro-4H-1,3,2-benzodioxaphosphorin-4-one (56.7 mg, 0.28 mmol) according the procedure of Shadid, B. et al., Tetrahedron, 1989, 45, 12, 3889. After 10 minutes, another portion of 2-chloro-4H-1,3,2-benzodioxaphosphorin-4-one (40 mg, 0.20 mmol) and DIEA (35 μL, 0.20 mmol) were added. The reaction was allowed to proceed at room temperature for an additional hour, after which it was quenched by the addition of H2O. The solution was stirred for another 10 minutes and concentrated in vacuo to a small volume. The product was triturated with diethyl ether and coevaporated from acetonitrile (4×10 mL) to provide the product. 1H NMR (300 MHz, CDCl3) δ 0.03 (s, 9H), 1.08-1.30 (m, 2H), 1.84 (br s, 3H), 2.17 (s, 3H), 3.46 (br s, 2H), 3.76 (s, 3H), 4.21-4.39 (m, 4H), 5.12 (s, 2H), 5.43-5.60 (m, 1H), 7.83 (br s, 1H); 31P (121.4 MHz, CDCl3) δ 7.22; MS (m/z) 441 [M−H]−.

Workup

  1. waitto proceed at room temperature for an additional hour
  2. customafter which it was quenched by the addition of H2O
  3. concentrationconcentrated in vacuo to a small volume
  4. customThe product was triturated with diethyl ether
  5. customto provide the product

Sources & evidence

ORD record
ord-cace19f868a342219338aa077f4899d2
Source dataset
uspto-grants-2008_11
Patent number
US07452901B2

Linked notes

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