Bromotrimethylsilane → [2-[2-(2-Methoxyethoxy)ethoxy]ethyl]phosphonic acid

HRID 1952416ノート

反応式

HRID 1952416 の反応式
C([O:3][P:4]([CH2:9][CH2:10][O:11][CH2:12][CH2:13][O:14][CH2:15][CH2:16][O:17][CH3:18])(=[O:8])[O:5]CC)C.Br[Si](C)(C)C>C(Cl)Cl.CO>[CH3:18][O:17][CH2:16][CH2:15][O:14][CH2:13][CH2:12][O:11][CH2:10][CH2:9][P:4](=[O:3])([OH:8])[OH:5]

参加物

5

反応物 2

HCID 76113BromotrimethylsilaneHCID 866385191-[2-(2-Diethoxyphosphorylethoxy)ethoxy]-2-methoxy-ethane

生成物 1

HCID 24899678[2-[2-(2-Methoxyethoxy)ethoxy]ethyl]phosphonic acid

試薬・触媒・溶媒 2

HCID 887Methanol溶媒HCID 6344Dichloromethane溶媒2 回

反応条件

温度
-35 °C

実験手順

{2-[2-(2-Methoxyethoxy)ethoxy]ethyl}phosphonic acid diethyl ester (1.00 g, 3.5 mmol) was dissolved in CH2Cl2 (20 ml) under N2. Bromotrimethylsilane (2.3 ml, 17.5 mmol) was added via syringe and the mixture was stirred for 2 hours. Volatiles were removed in vacuo to give a thick orange oil; this was dissolved in MeOH (100 ml) with fuming to give a give a yellow solution. The mixture was stirred for 2 hours and evaporated to dryness to give a thick yellow oil which was dissolved in CH2Cl2 and extracted with NaOH (3×50 ml, aq., 1M). HCl (conc.) was added to the yellow aqueous layer until the solution was acidic to pH paper. Removal of water in vacuo gave a yellow crystalline solid that was extracted with EtOH and filtered. Cooling the filtrate to −35° C. resulted in precipitation of further white solid which was removed by filtration. Removal of volatiles from the yellow supernatant under vacuum (0.01 torr) afforded the desired product as a thick yellow oil. Yield 0.60 g, 2.6 mmol, 74%. 1H NMR (d6-DMSO, 400 MHz, 298 K): δ 3.55 (ap. q. J=7 Hz, 2H), 3.48 (m, 6H), 3.41 (m, 2H), 3.23 (s, 3H), 1.83 (d of t, JH-P=19 Hz, JH-H=7 Hz, 2H). 13C{1H} NMR (d6-DMSO, 100 MHz, 298 K): δ 71.25, 69.69, 69.58, 69.27, 65.41, 58.05, 28.99 (d, JC-P=132 Hz). 31P{1H} NMR (d6-DMSO, 162 MHz, 298 K): δ 23.15. MS (ESI, m/z): 227 (44−, 100%), 229 ([M+H]+, 10%). Exact mass found (calculated for [M+H]+, m/z): 229.08490 (229.08410).

後処理

  1. customVolatiles were removed in vacuo
  2. customto give a thick orange oil
  3. customto give
  4. customa give a yellow solution
  5. stirringThe mixture was stirred for 2 hours
  6. customevaporated to dryness
  7. customto give a thick yellow oil which
  8. extractionextracted with NaOH (3×50 ml, aq., 1M)
  9. additionHCl (conc.) was added to the yellow aqueous layer until the solution
  10. customRemoval of water in vacuo
  11. customgave a yellow crystalline solid
  12. extractionthat was extracted with EtOH
  13. filtrationfiltered
  14. customresulted in precipitation of further white solid which
  15. customwas removed by filtration
  16. customRemoval of volatiles from the yellow supernatant under vacuum (0.01 torr)

出典と根拠

ORDレコード
ord-5001339a66b742199890cf9800d7d3c3
出典データセット
uspto-grants-2013_03
特許番号
US08405069B2

反応ノート

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