Methyl chloroformate → HCID 23359463, compound

HRID 1087804Notes

Reaction equation

HRID 1087804 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[Cl:13][C:14]1[CH:15]=[CH:16][C:17]2[C:25]3[CH:21]([CH2:22][N:23]([C:26]([NH:28][C:29]4[CH:34]=[CH:33][C:32]([C:35]([F:38])([F:37])[F:36])=[CH:31][CH:30]=4)=[O:27])[N:24]=3)[CH2:20][CH2:19][C:18]=2[CH:39]=1.Cl[C:41]([O:43][CH3:44])=[O:42]>CCCCCC.C1COCC1>[Cl:13][C:14]1[CH:15]=[CH:16][C:17]2[C:25]3[C:21]([C:41]([O:43][CH3:44])=[O:42])([CH2:22][N:23]([C:26]([NH:28][C:29]4[CH:34]=[CH:33][C:32]([C:35]([F:37])([F:36])[F:38])=[CH:31][CH:30]=4)=[O:27])[N:24]=3)[CH2:20][CH2:19][C:18]=2[CH:39]=1

Participants

7

Reactant 4

HCID 6586Methyl chloroformateHCID 7912DiisopropylamineHCID 23359466HCID 23359466, compoundHCID 178418339Butyllithium

Product 1

HCID 23359463HCID 23359463, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

A solution of 50 ml of THF and 6.7 ml of diisopropylamine was cooled under N2 to -78° C. and then 17.5 ml of 2.5 M n-butyllithium in hexane was added. After 5 min. a solution of 7.8 g of the title compound of Example 4 in 15 ml of THF was added dropwise and the dark red solution that formed was stirred at -78° C. for an additional 15 min. After this time a solution of 4.6 ml of methyl chloroformate in 10 ml of THF was added dropwise and the red color dissipated rapidly. The reaction was warmed to room temperature and after 1 hr quenched with 5% aqueous sodium bicarbonate. The reaction mixture was partitioned between ether and 5% aqueous sodium bicarbonate. The ether extracts were dried over magnesium sulfate and concentrated to 14.1 g of a yellow oily solid. The crude product was triturated with ether and the resulting white precipitate was filtered and dried to afford 5.56 g of the title compound as a white solid, m.p. 234° C. to 236° C. 1H NMR(CDCl3) δ 2.1 (m, 1H), 2.75 (m, 1H) 2.95 (m, 2H), 3.71 (s, 3H), 3.75 (d, 1H, J=6Hz), 4.59 (d, 1H, J=6Hz), 7.25 (m, 2H), 7.57 (d, 2H), 7.66 (d, 2H), 7.94 (d, 1H), 8.18 (d, 1H),

Workup

  1. customthe dark red solution that formed
  2. temperatureThe reaction was warmed to room temperature and after 1 hr
  3. customquenched with 5% aqueous sodium bicarbonate
  4. customThe reaction mixture was partitioned between ether and 5% aqueous sodium bicarbonate
  5. dry with materialThe ether extracts were dried over magnesium sulfate
  6. concentrationconcentrated to 14.1 g of a yellow oily solid
  7. customThe crude product was triturated with ether
  8. filtrationthe resulting white precipitate was filtered
  9. customdried

Sources & evidence

ORD record
ord-fc5c84973e8543558ee63fb5fdedc0eb
Source dataset
uspto-grants-1990_10
Patent number
US04960784

Reaction notes

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