Ammonium Chloride → Ethyl 4-(2,6-dimethoxyphenyl)-4-(1,1-dimethylethylsulfinamido)-2-methylbutanoate

HRID 594337Notes

Reaction equation

HRID 594337 reaction equation
I[C:2]1[C:7]([O:8][CH3:9])=[CH:6][CH:5]=[CH:4][C:3]=1[O:10][CH3:11].[Li]CCCC.[C:17]([S:21]([N:23]=[CH:24][CH2:25][CH:26]([CH3:32])[C:27]([O:29][CH2:30][CH3:31])=[O:28])=[O:22])([CH3:20])([CH3:19])[CH3:18].[NH4+].[Cl-]>C1COCC1.O.CCOCC>[CH3:11][O:10][C:3]1[CH:4]=[CH:5][CH:6]=[C:7]([O:8][CH3:9])[C:2]=1[CH:24]([NH:23][S:21]([C:17]([CH3:19])([CH3:18])[CH3:20])=[O:22])[CH2:25][CH:26]([CH3:32])[C:27]([O:29][CH2:30][CH3:31])=[O:28]

Participants

8

Reactant 4

HCID 25517Ammonium ChlorideHCID 113914072-Iodo-1,3-dimethoxybenzeneHCID 86695624Ethyl 4-((tert-butylsulfinyl)imino)-2-methylbutanoateHCID 178418339Butyllithium

Product 1

HCID 86695625Ethyl 4-(2,6-dimethoxyphenyl)-4-(1,1-dimethylethylsulfinamido)-2-methylbutanoate

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

A cooled (−78° C.) yellow solution of 2-iodo-1,3-dimethoxybenzene (8.553 g; 32.39 mmol) in anh. THF (175 ml), under nitrogen, was treated dropwise with a solution of 1.6 M n-BuLi in hexanes (20.25 ml; 32.40 mmol). The resulting slightly yellow solution was further stirred at −78° C. for 15 min. A yellow solution of ethyl 4-((tert-butylsulfinyl)imino)-2-methylbutanoate (6.410 g; 25.91 mmol) in anh. THF (15 ml) was then added dropwise to the cooled reaction mixture, and stirring at −78° C. was continued for 30 min. The resulting yellow reaction mixture was treated successively with aq. sat. NH4Cl (80 ml), Et2O (250 ml) and water (75 ml). The separated yellow organic layer was then washed with brine (75 ml), dried over anh. MgSO4, filtered, and concentrated to dryness under reduced pressure. Purification by FC (DCM/MeOH=25/1) afforded ethyl 4-(2,6-dimethoxyphenyl)-4-(1,1-dimethylethylsulfinamido)-2-methylbutanoate as an orange oil. LC-MS (conditions B): tR=0.88 min. and [M+H]+: 386.15 g/mol; tR=0.89 min. and [M+H]+: 386.14 g/mol (mixture of diastereoisomers).

Workup

  1. stirringstirring at −78° C.
  2. waitwas continued for 30 min
  3. washThe separated yellow organic layer was then washed with brine (75 ml)
  4. dry with materialdried over anh. MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated to dryness under reduced pressure
  7. customPurification by FC (DCM/MeOH=25/1)

Sources & evidence

ORD record
ord-c189b82b709c4118b7ed09deaeae51aa
Source dataset
uspto-grants-2016_01
Patent number
US09242970B2

Reaction notes

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