Sulfuric Acid → Dimethyl (6-methyl-2-oxoheptyl)phosphonate

HRID 28786

反応式

HRID 28786 の反応式
[CH3:1][P:2](=[O:7])([O:5][CH3:6])[O:3][CH3:4].[Li]CCCC.[CH3:13][CH:14]([CH3:22])[CH2:15][CH2:16][CH2:17][C:18](OC)=[O:19].CC(C)CCCC(O)=O.S(=O)(=O)(O)O>C1COCC1.CO>[CH3:13][CH:14]([CH3:22])[CH2:15][CH2:16][CH2:17][C:18](=[O:19])[CH2:1][P:2](=[O:7])([O:5][CH3:6])[O:3][CH3:4]

参加物

8

反応物 5

HCID 1118Sulfuric AcidHCID 123445-Methylhexanoic acidHCID 12958Dimethyl methylphosphonateHCID 519894Methyl 5-methylhexanoateHCID 178418339Butyllithium

生成物 1

HCID 15223968Dimethyl (6-methyl-2-oxoheptyl)phosphonate収率 76.2%

試薬・触媒・溶媒 2

HCID 887Methanol溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

To a solution of dimethyl methylphosphonate (2.17 ml, 20 mmol) in anhydrous THF (20 mL), cooled at −78° C. was added n-BuLi (1.6 M in hexane, 13.7 mL, 22 mmol). The mixture was stirred for 30 minutes at this temperature under nitrogen. Methyl 5-methylhexanoate (1.44 g, 10 mmol), prepared from 5-methylhexanoic acid (from Avocado) and methanol at the presence of the catalytic amount of the concentrated sulfuric acid (the procedure described in Intermediate 17.1), was added dropwise for 10 minutes. The mixture was stirred for 2 hours at −78° C., gradually was warm to room temperature. The mixture was quenched with addition of 1N HCl to pH 4-5. The organic layer was separated, washed with brine and dried over MgSO4. The residue was purified through flash chromatography on silica gel (EtOAc:Hexanes=1:1) to give the product (1.80 g) with colorless oil in 76% yield. 1HNMR (CD3OD, ppm) δ 0.866 (d, J=6.5 Hz, 6H), 1.16 (m, 2H), 1.56 (m, 3H), 2.58 (t, J=7.3 Hz, 2H), 3.10 (d, J=22.7 Hz, 2H), 3.70 (s, 3H), 3.79 (s, 3H)

後処理

  1. additionwas added dropwise for 10 minutes
  2. stirringThe mixture was stirred for 2 hours at −78° C.
  3. customThe mixture was quenched with addition of 1N HCl to pH 4-5
  4. customThe organic layer was separated
  5. washwashed with brine
  6. dry with materialdried over MgSO4
  7. customThe residue was purified through flash chromatography on silica gel (EtOAc:Hexanes=1:1)

出典と根拠

ORDレコード
ord-002ca54a27b442f1985da6a42793eac5
出典データセット
uspto-grants-2008_09
特許番号
US07419999B2

関連ノート

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