Triethylamine → 3-[[2,6-bis(1,1-dimethylethyl)-4H-selenopyran-4-ylidene]methyl]-2,4,4-trichlorocyclobut-2-en-1-one

HRID 484472

Reaction equation

HRID 484472 reaction equation
C(N(CC)CC)C.F[B-](F)(F)F.[CH3:13][C:14]([C:17]1[CH:22]=[C:21]([CH3:23])[CH:20]=[C:19]([C:24]([CH3:27])([CH3:26])[CH3:25])[Se+:18]=1)([CH3:16])[CH3:15].[Cl:28][C:29]1[C:30](=[O:36])[C:31]([Cl:35])([Cl:34])[C:32]=1Cl.[OH-].[Na+]>ClCCl>[CH3:16][C:14]([C:17]1[Se:18][C:19]([C:24]([CH3:27])([CH3:26])[CH3:25])=[CH:20][C:21](=[CH:23][C:32]2[C:31]([Cl:35])([Cl:34])[C:30](=[O:36])[C:29]=2[Cl:28])[CH:22]=1)([CH3:13])[CH3:15]

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 14798Sodium HydroxideHCID 185452,3,4,4-Tetrachloro-2-cyclobuten-1-oneHCID 120389182,6-Bis(1,1-dimethylethyl)-4-methylselenopyrylium tetrafluoroborate

Product 1

HCID 120389193-[[2,6-bis(1,1-dimethylethyl)-4H-selenopyran-4-ylidene]methyl]-2,4,4-trichlorocyclobut-2-en-1-oneYield 71.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of triethylamine (14.8 g, 147 mmol) in dichloromethane (40 mL) was added dropwise under nitrogen to a solution of 2,6-bis(1,1-dimethylethyl)-4-methylselenopyrylium tetrafluoroborate (26.2 g, 73.4 mmol, prepared in Examples 4 and 5 above) and 2,3,4,4-tetrachlorocyclobut-2-en-1-one (15.2 g, 73.4 mmol) in dichloromethane (60 mL), contained in a flask equipped with a condenser and an outlet connected to a gas-washing bottle containing 10% aqueous sodium hydroxide solution; the addition was effected at a rate such that the temperature of the reaction mixture did not exceed 35° C. After the addition had been completed, the reaction mixture was stirred for one hour, then applied to a column packed with silica gel. Elution with dichloromethane, followed by evaporation of the solvent under reduced pressure, provided the crude product which was further purified by trituration with trifluoroethanol for one hour to give 3-[[2,6-bis(1,1,-dimethylethyl)-4H-selenopyran-4-ylidene]methyl]-2,4,4-trichlorocyclobut-2-en-1-one (23 g, 71% yield) as maroon crystals. The structure of this compound was confirmed by mass spectroscopy and by 1H and 13C NMR spectroscopy.

Workup

  1. customcontained in a flask
  2. customequipped with a condenser and an outlet
  3. additionthe addition
  4. customdid not exceed 35° C
  5. additionAfter the addition
  6. washElution with dichloromethane
  7. customfollowed by evaporation of the solvent under reduced pressure
  8. customprovided the crude product which
  9. customwas further purified by trituration with trifluoroethanol for one hour

Sources & evidence

ORD record
ord-f35a6d18a5f44a41a5981bb95fc6dc03
Source dataset
uspto-grants-1993_07
Patent number
US05231190

Linked notes

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