1,2-Dimethoxyethane → HCID 10610177, compound

HRID 1860692Notes

Reaction equation

HRID 1860692 reaction equation
[H-].[Na+].C(COC)OC.[C:9]([O:13][CH2:14][CH2:15][O:16][CH2:17][CH2:18][OH:19])([CH3:12])([CH3:11])[CH3:10].C(OCCOCCO[C:29]([F:33])=[C:30]([F:32])[F:31])C>CCCCC.C1OCCOCCOCCOCCOCCOC1>[C:9]([O:13][CH2:14][CH2:15][O:16][CH2:17][CH2:18][O:19][C:29]([F:33])=[C:30]([F:32])[F:31])([CH3:12])([CH3:11])[CH3:10]

Participants

7

Reactant 4

HCID 80711,2-DimethoxyethaneHCID 24758Sodium hydrideHCID 101978372-(2-t-butoxyethoxy)ethanolHCID 10680116Ethene, [2-(2-ethoxyethoxy)ethoxy]trifluoro-

Product 1

HCID 10610177HCID 10610177, compoundYield 63%

Reagents, catalysts & solvents 2

HCID 2855718-Crown-6CatalystHCID 8003PentaneSolvent

Conditions

Temperature
65 °C

Procedure

Bu-TFVE was prepared by mixing 2.66 g of NaH (0.111 mol) and 1 g of 18-crown-6 with 135 mL of glyme under inert atmosphere at 65° C. 15.0 g (0.092 mol) of 2-(2-t-butoxyethoxy)ethanol was slowly added to the flask and stirred at 65° C. 1 h. The alkoxide was transferred to the dry 300 mL Parr reactor, stirred and heated at 65° C. for 1 h after which TFE gas was added. The pressure was maintained at ˜50-60 PSI. A very slight exotherm (˜5° C.) was initially observed. After 45 minutes, stirring was stopped and the reactor was cooled to room temperature. Excess TFE was carefully vented and the reactor contents transferred to a 500 mL Erlenmeyer flask. The mixture was diluted to 300 mL with pentane to effect complete precipitation of sodium salts. The mixture was filtered through a course frit funnel to remove sodium salts. The liquid fraction was rotary evaporated to give a clear yellow crude product. The crude product was vacuum fractionally distilled over potassium carbonate. 14.1 g (63% yield) of the desired product, 1-[2-(2-ethoxyethoxy)ethoxy]-1,2,2-trifluoroethene, was isolated at a boiling point of 26-27° C. (pressure 0.15 mmHg, >99% purity by GC). 19F NMR: δ=−123.5 (dd, 1F J=56, 104 Hz, CF), −130.3 (dd, 1F J=104, 108, CF), −135.1 (dd, 1F J=56, 108 Hz, CF); 1H NMR: δ=4.15 (m, 2H, CFOCF2), 3.75 (t, 2H, OCH2), 3.65-3.45 (m, 4H, OCH2), 1.2(s, 9H, C(CH3)3).

Workup

  1. customBu-TFVE was prepared
  2. custom1 h
  3. stirringstirred
  4. temperatureheated at 65° C. for 1 h after which TFE gas
  5. additionwas added
  6. temperatureThe pressure was maintained at ˜50-60 PSI
  7. customA very slight exotherm (˜5° C.)
  8. stirringstirring
  9. temperaturethe reactor was cooled to room temperature
  10. customprecipitation of sodium salts
  11. filtrationThe mixture was filtered through a course frit funnel
  12. customto remove sodium salts
  13. customThe liquid fraction was rotary evaporated
  14. customto give a clear yellow crude product
  15. distillationfractionally distilled over potassium carbonate

Sources & evidence

ORD record
ord-86aeca71ff8244dca42fd71697929427
Source dataset
uspto-grants-2003_03
Patent number
US06531558B1

Reaction notes

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