Isopropyl chloroformate → HCID 22884175, compound

HRID 1598439Notes

Reaction equation

HRID 1598439 reaction equation
Cl.[CH3:2][NH:3][O:4][CH3:5].CN1CCOCC1.[C:13]([O:17][C:18]([NH:20][C@H:21]([CH2:25][C:26]([C:39]1[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=1)([C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)[C:22](O)=[S:23])=[O:19])([CH3:16])([CH3:15])[CH3:14].C(OC(Cl)=O)(C)C>ClCCl.O1CCCC1>[CH3:5][O:4][N:3]([CH3:2])[C:22](=[S:23])[C@H:21]([NH:20][C:18]([O:17][C:13]([CH3:15])([CH3:14])[CH3:16])=[O:19])[CH2:25][C:26]([C:39]1[CH:40]=[CH:41][CH:42]=[CH:43][CH:44]=1)([C:33]1[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=1)[C:27]1[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=1

Participants

7

Reactant 4

HCID 7917Isopropyl chloroformateHCID 79724-Methylmorpholine3×HCID 81138Methanamine, N-methoxy-, hydrochloride (1:1)2×HCID 178454172HCID 178454172, compound

Product 1

HCID 22884175HCID 22884175, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent3×HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-30 °C

Procedure

The title compound was synthesized essentially according to the procedure described by O. P. Goel, U. Krolls, M. Stier, and S. Kesten in Organic Syntheses, 1988, 67, 69-75. Thus N,O-dimethyl-hydroxylamine hydrochloride (1.05 g, 10.82 mmol) and N-methyl-morpholine (1.22 mL, 11.14 mmol) were stirred in dichloromethane (6 mL) under nitrogen at 0° C. for 30 min. In a separate flask, 2(R)-tert-butoxycarbonylamino-3-triphenylmethyl-thiopropionic acid (5.02 g, 10.82 mmol) in tetrahydrofuran (11.5 mL, dry) and methylene chloride (45 mL) were cooled to -20° C., and N-methylmorpholine (1.22 mL, 11.14 mmol) and isopropylchloroformate (10.82 mL of 1M solution in toluene) were added via syringe, maintaining the temperature less than -15° C. The reaction was stirred at -30° C., and the suspension of N,O-dimethylhydroxylamine hydrochloride and N-methylmorpholine in methylene chloride added all at once. The cooling bath was removed and the reaction allowed to warm to room temperature over 4 h. The reaction was cooled to 0° C. and quickly washed with two portions of 0.2N hydrochloric acid, two portions of 0.5N sodium hydroxide, and saturated sodium chloride solution. The organic phase was dried over magnesium sulfate, filtered and reduced in vacuo to obtain the title compound as a clear gum, 5.50 g. NMR (300 MHz, DMSO-d6) δ 7.30 (15H, m), 4.43 (1H, br s), 3.56 (3H, s), 2.99 (3H, s), 2.30 (2H, m), 1.36 (9H, s).

Workup

  1. customThe title compound was synthesized essentially
  2. temperaturemaintaining the temperature less than -15° C
  3. additionadded all at once
  4. customThe cooling bath was removed
  5. temperatureto warm to room temperature over 4 h
  6. temperatureThe reaction was cooled to 0° C.
  7. washquickly washed with two portions of 0.2N hydrochloric acid, two portions of 0.5N sodium hydroxide, and saturated sodium chloride solution
  8. dry with materialThe organic phase was dried over magnesium sulfate
  9. filtrationfiltered

Sources & evidence

ORD record
ord-41ba9f28a72a4ab2ae9a0aa9604223c3
Source dataset
uspto-grants-1998_04
Patent number
US05736539

Reaction notes

Loading…