Isobutyl chloroformate → HCID 54506020, compound

HRID 1741662Notes

Reaction equation

HRID 1741662 reaction equation
[NH:1]1[C:9]2[C:4](=[CH:5][CH:6]=[CH:7][CH:8]=2)[CH:3]=[C:2]1[CH2:10][CH:11]([OH:15])[C:12]([OH:14])=O.O([Si](C(C)(C)C)(C)C)S(C(F)(F)F)(=O)=O.C(OC(Cl)=O)C(C)C.[F:39][C:40]([F:54])([F:53])[C:41]1[CH:42]=[C:43]([CH:46]=[C:47]([C:49]([F:52])([F:51])[F:50])[CH:48]=1)[CH2:44][NH2:45].[F-].C([N+](CCCC)(CCCC)CCCC)CCC>ClCCl.O1CCCC1.C(N(CC)CC)C>[F:39][C:40]([F:53])([F:54])[C:41]1[CH:42]=[C:43]([CH:46]=[C:47]([C:49]([F:52])([F:50])[F:51])[CH:48]=1)[CH2:44][NH:45][C:12](=[O:14])[CH:11]([CH2:10][C:2]1[NH:1][C:9]2[C:4]([CH:3]=1)=[CH:5][CH:6]=[CH:7][CH:8]=2)[OH:15]

Participants

9

Reactant 5

HCID 62365Isobutyl chloroformateHCID 123564tert-Butyldimethylsilyl trifluoromethanesulphonateHCID 5210993,5-Bis(trifluoromethyl)benzylamineHCID 2724141Tetrabutylammonium FluorideHCID 53700591HCID 53700591, compound

Product 1

HCID 54506020HCID 54506020, compound

Reagents, catalysts & solvents 3

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent2×

Procedure

Indolelactic acid (2.0 g) suspended in dichloromethane (25 ml) was treated with triethylamine (2.8 ml) and tertbutyldimethylsilyl triflate (2.3 ml) for 16 hours. Triethylamine (2 ml) was then added followed by iso-butylchloroformate (1.5 ml). After stirring for 30 minutes 3,5-bistrifluoromethylbenzylamine (2.5 g) was added and the reaction stirred a further 2 hours. The mixture was washed with 2N hydrochloric acid, aqueous sodium bicarbonate and water, then dried (Na2SO4) and concentrated. Chromatography on silica gel, eluting with ethyl acetate-petroleum ether (1:3) gave an oil which was treated with tetrabutylammonium fluoride (20 ml of a 1M solution in tetrahydrofuran) for 16 hours. The solution was concentrated, diluted with dichloromethane, washed with water, dried and concentrated. The residue was purified by chromatography (eluting with ethyl acetate-petroleum ether), followed by crystallisation from diethyl ether-petroleum ether to give the title compound as a white crystalline solid, mp 119° C.; found: C, 56.08; H, 3.85; N, 6.43; C20H 16 F6N2O2 requires C, 55.82; H, 3.75; N, 6.51.

Workup

  1. additionwas added
  2. washThe mixture was washed with 2N hydrochloric acid, aqueous sodium bicarbonate and water
  3. dry with materialdried (Na2SO4)
  4. concentrationconcentrated
  5. washChromatography on silica gel, eluting with ethyl acetate-petroleum ether (1:3)
  6. customgave an oil which
  7. concentrationThe solution was concentrated
  8. additiondiluted with dichloromethane
  9. washwashed with water
  10. customdried
  11. concentrationconcentrated
  12. customThe residue was purified by chromatography (eluting with ethyl acetate-petroleum ether)
  13. customfollowed by crystallisation from diethyl ether-petroleum ether

Sources & evidence

ORD record
ord-a493f14624014b9f8e98eeabd6613b31
Source dataset
uspto-grants-1994_08
Patent number
US05334606

Reaction notes

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