tert-Butanol → HCID 18691539, compound

HRID 704639Notes

Reaction equation

HRID 704639 reaction equation
[CH:1]([CH:3]1[CH2:5][CH:4]1C(O)=O)=[CH2:2].C([N:11]([CH2:14]C)CC)C.C1([O:22]P(N=[N+]=[N-])(OC2C=CC=CC=2)=O)C=CC=CC=1.[C:35]([OH:39])([CH3:38])([CH3:37])[CH3:36]>C1(C)C=CC=CC=1>[C:35]([O:39][C:14]([NH:11][CH:4]1[CH2:5][CH:3]1[CH:1]=[CH2:2])=[O:22])([CH3:38])([CH3:37])[CH3:36]

Participants

6

Reactant 4

HCID 6386tert-ButanolHCID 8471TriethylamineHCID 123414Diphenylphosphoryl azide2×HCID 10942379Cyclopropanecarboxylic acid, 2-ethenyl-

Product 1

HCID 18691539HCID 18691539, compoundYield 38%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
70 °C

Procedure

2-Ethenylcyclopropanecarboxylic acid (14.42 g, 129 mmol) from Step B was dissolved in 100 mL of toluene at 0° C. Triethyl amine (19.79 mL) was added in one portion, followed by 30.5 mL of diphenylphosphonoazide (DPPA) added dropwise from an addition funnel. After the addition of DPPA was complete the reaction mixture was warmed to 70° C. and stirred at 70° C. for 45 minutes. tert-Butyl alcohol (50 mL) was added in one portion to the reaction mixture. The temperature of the reaction mixture was then raised to 100° C. and it was stirred overnight at this temperature. TLC analysis (on silica gel plates eluted with 25% ethyl acetate in hexane) showed no remaining starting material. The reaction mixture was diluted with 150 mL of methylene chloride, washed with 100 mL of 1M aqueous phosphoric acid solution, 100 mL of saturated sodium bicarbonate solution and 100 mL of saturated sodium chloride solution (brine), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The crude product was purified by column chromatography on silica gel eluted with 5% ethyl acetate in hexane. N-tert-Butoxycarbonyl-2-ethenylcyclopropylamine was obtained in 38% yield (8.97 g) as a clear colorless oil. 1H NMR (CDCl3) 0.90 (m, 2H), 1.45 (s, 9H), 1.5 (m, 1H), 2.50 (m, 1H), 4.97 (dd, 1H), 5.07 (dd, 1H), 5.51 (m, 1H).

Workup

  1. additionadded dropwise from an addition funnel
  2. temperatureThe temperature of the reaction mixture was then raised to 100° C.
  3. stirringit was stirred overnight at this temperature
  4. washTLC analysis (on silica gel plates eluted with 25% ethyl acetate in hexane)
  5. additionThe reaction mixture was diluted with 150 mL of methylene chloride
  6. washwashed with 100 mL of 1M aqueous phosphoric acid solution, 100 mL of saturated sodium bicarbonate solution and 100 mL of saturated sodium chloride solution (brine)
  7. dry with materialdried over anhydrous magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customThe crude product was purified by column chromatography on silica gel
  11. washeluted with 5% ethyl acetate in hexane

Sources & evidence

ORD record
ord-fa434d787456422fad68399afdb330f5
Source dataset
uspto-grants-1991_01
Patent number
US04988703

Reaction notes

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