Triethyl phosphite → Diethyl 3-(5-bromopyridin-2-yloxy)benzylphosphonate

HRID 1666371ノート

反応式

HRID 1666371 の反応式
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([O:8][C:9]2[CH:14]=[CH:13][CH:12]=[C:11]([CH2:15]Cl)[CH:10]=2)=[N:6][CH:7]=1.[CH2:17]([O:19][P:20]([O:24]CC)[O:21][CH2:22][CH3:23])[CH3:18]>CCCCCCC>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([O:8][C:9]2[CH:10]=[C:11]([CH:12]=[CH:13][CH:14]=2)[CH2:15][P:20](=[O:24])([O:21][CH2:22][CH3:23])[O:19][CH2:17][CH3:18])=[N:6][CH:7]=1

参加物

4

反応物 2

HCID 31215Triethyl phosphiteHCID 198462395-Bromo-2-(3-(chloromethyl)phenoxy)pyridine

生成物 1

HCID 86623897Diethyl 3-(5-bromopyridin-2-yloxy)benzylphosphonate収率 81.3%

試薬・触媒・溶媒 1

HCID 8900Heptane溶媒

反応条件

温度
150 °C

実験手順

5-Bromo-2-(3-(chloromethyl)phenoxy)pyridine (3.08 g, 10.3 mmol) from Step 2 was treated neat with triethylphosphite (2.65 mL, 15.5 mmol) and heated to 150° C. After 5 h, the reaction mixture was removed from the heating bath and treated slowly with heptane until an oil precipitated out of solution. Ethyl acetate was added until mixture became homogenous. Heptane was slowly added again (at a cooler temperature) until a white precipitate formed. After the addition of more heptane and stirring for 15 min, the precipitate was filtered to afford a white solid (3.35 g, 81% yield). MS (APCI) M+1=400.0; 1H NMR (400 MHz, CDCl3) δ ppm 1.26 (t, J=7.02 Hz, 6H) 3.17 (d, J=21.64 Hz, 2H) 3.98-4.08 (m, 4H) 6.84 (d, J=8.77 Hz, 1H) 7.00-7.05 (m, 1H) 7.08 (q, J=2.21 Hz, 1H) 7.15-7.20 (m, 1H) 7.35 (t, J=7.90 Hz, 1H) 7.77 (dd, J=8.58, 2.53 Hz, 1H) 8.21 (d, J=2.73 Hz, 1H).

後処理

  1. customthe reaction mixture was removed from the heating bath
  2. additiontreated slowly with heptane until an oil
  3. customprecipitated out of solution
  4. additionEthyl acetate was added until mixture
  5. additionHeptane was slowly added again (at a cooler temperature) until a white precipitate
  6. customformed
  7. filtrationthe precipitate was filtered

出典と根拠

ORDレコード
ord-5f26e7f4a24d44ea9d26168db142fb63
出典データセット
uspto-grants-2011_10
特許番号
US08044052B2

反応ノート

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