Tert-Butylamine → HCID 15711867, compound

HRID 982106Notes

Reaction equation

HRID 982106 reaction equation
[Br:1]Br.C(N)(C)(C)C.[C:8]([CH:10]1[C:15]2[CH:16]=[CH:17][CH:18]=[C:19]([OH:20])[C:14]=2[CH2:13][CH:12]([C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[O:11]1)#[N:9]>C1(C)C=CC=CC=1.C(Cl)Cl>[Br:1][C:18]1[CH:17]=[CH:16][C:15]2[CH:10]([C:8]#[N:9])[O:11][CH:12]([C:21]3[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=3)[CH2:13][C:14]=2[C:19]=1[OH:20].[Br:1][C:18]1[CH:17]=[CH:16][C:15]2[C@H:10]([C:8]#[N:9])[O:11][C@H:12]([C:21]3[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=3)[CH2:13][C:14]=2[C:19]=1[OH:20]

Participants

7

Reactant 3

HCID 6385Tert-ButylamineHCID 24408BromineHCID 15711866HCID 15711866, compound

Product 2

HCID 15711867HCID 15711867, compoundYield 75%HCID 20069094HCID 20069094, compound

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
-78 °C

Procedure

Bromine (0.11 mL, 2.1 mmol) was added to a solution of 0.91 mL (8.7 mmol) of t-butylamine in 15 mL of toluene at 31 30° C. The resultant mixture was stirred at -30° C. for 10 minutes, cooled to -78° C. and then treated with a solution of 1.09 g (4.3 mmol) of 1-cyano-3,4-dihydro -5-hydroxy-3-phenyl-1H-2-benzopyran, from Step 3, in 15 mL of methylene chloride. The reaction mixture was stirred at -78° C. for 3 h, allowed to slowly warm to ambient temperature over a 3 h period and then partitioned between ethyl acetate and water. The organic extract was washed with water and brine, dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The residue was purified on silica gel eluted with 1% ethyl acetate in hexane to give 0.32 g (24% yield) of [1 R, 3 R]-6-bromo-1-cyano-3,4-dihydro-5-hydroxy-3-phenyl-1H-2-benzopyran and 0.26 g (20% yield) of [1R,3S] 6-bromo-1-cyano-3,4-dihydro-5-hydroxy-3-phenyl-1H-2-benzopyran.

Workup

  1. temperatureto slowly warm to ambient temperature over a 3 h period
  2. custompartitioned between ethyl acetate and water
  3. extractionThe organic extract
  4. washwas washed with water and brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe residue was purified on silica gel
  9. washeluted with 1% ethyl acetate in hexane

Sources & evidence

ORD record
ord-7f057501c92b43e6be5606ae2431f8a1
Source dataset
uspto-grants-1991_02
Patent number
US04994486

Reaction notes

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