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 33025

反応式

HRID 33025 の反応式
[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]

参加物

5

反応物 3

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

生成物 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

試薬・触媒・溶媒 1

HCID 312751,4-Dioxane溶媒

実験手順

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]−.

後処理

  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

出典と根拠

ORDレコード
ord-7860f7d713fb46db995842b405555cdb
出典データセット
uspto-grants-2008_09
特許番号
US07427636B2

関連ノート

読み込み中…