Hydrochloric Acid → (S)-tert-butyl 1-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-1-oxopropan-2-ylcarbamate

HRID 1098786Notes

Reaction equation

HRID 1098786 reaction equation
CON(C)[C:4](=[O:15])[C@@H:5]([NH:7][C:8](=[O:14])[O:9][C:10]([CH3:13])([CH3:12])[CH3:11])[CH3:6].C([Mg]Cl)(C)C.[O:22]1[CH2:27][CH2:26][O:25][C:24]2[CH:28]=[C:29]([Mg]Br)[CH:30]=[CH:31][C:23]1=2.Cl>C1COCC1.COC(C)(C)C.O>[O:22]1[CH2:27][CH2:26][O:25][C:24]2[CH:28]=[C:29]([C:4](=[O:15])[C@@H:5]([NH:7][C:8](=[O:14])[O:9][C:10]([CH3:11])([CH3:12])[CH3:13])[CH3:6])[CH:30]=[CH:31][C:23]1=2

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 11806530(S)-tert-Butyl (1-(methoxy(methyl)amino)-1-oxopropan-2-yl)carbamateHCID 178418918HCID 178418918, compoundHCID 178419614HCID 178419614, compound

Product 1

HCID 59339713(S)-tert-butyl 1-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-1-oxopropan-2-ylcarbamate

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent3×HCID 15413tert-Butyl methyl etherSolvent2×

Conditions

Temperature
-17.5 °C

Procedure

A suspension of (S)-tert-butyl 1-(methoxy(methyl)amino)-1-oxopropan-2-ylcarbamate (3 g, 12.92 mmol) in THF (30 mL) was placed under a protective atmosphere of Argon and cooled down to −15 to −20° C., isopropylmagnesium chloride, 2M in THF (6.5 mL, 13.00 mmol) was added keeping the temperature below −10° C. The slurry started to dissolve, temperature was allowed to reach 0° C., a freshly prepared solution of (2,3-dihydrobenzo[b][1,4]dioxin-6-yl)magnesium bromide, 0.7M in THF (20 mL, 14.00 mmol) was added. The temperature was allowed to reach r.t., the reaction mixture was stirred for 17 h. 1N HCl (300 mL) was cooled on ice bath to +10° C., the reaction mixture was poured into the acidic water solution, TBME=tert-butyl methyl ether (300 mL) was added and the mixture was transferred to a separation funnel. The water phase was back extracted with TBME (200 mL). The ether phases were washed with water, brine and dried (Na2SO4).

Workup

  1. customthe temperature below −10° C
  2. dissolutionto dissolve
  3. customto reach 0° C.
  4. customto reach r.t.
  5. additionwas added
  6. customthe mixture was transferred to a separation funnel
  7. extractionThe water phase was back extracted with TBME (200 mL)
  8. washThe ether phases were washed with water, brine
  9. dry with materialdried (Na2SO4)

Sources & evidence

ORD record
ord-ff7eda6ce2d84c0fbee9354a75686f76
Source dataset
uspto-grants-2012_03
Patent number
US08143290B2

Reaction notes

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