Ammonium Chloride → Methyl 6-(3,5-dimethoxypyridin-4-yl)-6-(1,1-dimethylethylsulfinamido)hexanoate

HRID 594344Notes

Reaction equation

HRID 594344 reaction equation
Br[C:2]1[C:7]([O:8][CH3:9])=[CH:6][N:5]=[CH:4][C:3]=1[O:10][CH3:11].[Li]CCCC.[C:17]([S:21]([N:23]=[CH:24][CH2:25][CH2:26][CH2:27][CH2:28][C:29]([O:31][CH3:32])=[O:30])=[O:22])([CH3:20])([CH3:19])[CH3:18].[NH4+].[Cl-]>C1COCC1.O.CCOCC>[CH3:11][O:10][C:3]1[CH:4]=[N:5][CH:6]=[C:7]([O:8][CH3:9])[C:2]=1[CH:24]([NH:23][S:21]([C:17]([CH3:20])([CH3:19])[CH3:18])=[O:22])[CH2:25][CH2:26][CH2:27][CH2:28][C:29]([O:31][CH3:32])=[O:30]

Participants

8

Reactant 4

HCID 25517Ammonium ChlorideHCID 592006524-Bromo-3,5-dimethoxypyridineHCID 86695622Methyl 6-((tert-butylsulfinyl)imino)hexanoateHCID 178418339Butyllithium

Product 1

HCID 69083411Methyl 6-(3,5-dimethoxypyridin-4-yl)-6-(1,1-dimethylethylsulfinamido)hexanoate

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

A cooled (−78° C.) solution of commercially available 4-bromo-3,5-dimethoxypyridine (4.998 g; 22.92 mmol) in anh. THF (90 ml), under nitrogen, was treated dropwise with a solution of 1.6 M n-BuLi in hexanes (14.30 ml; 22.88 mmol). The resulting solution was further stirred at −78° C. for 10 min. A solution of methyl 6-((tert-butylsulfinyl)imino)hexanoate (3.780 g; 15.28 mmol) in anh. THF (10 ml) was then added to the cooled reaction mixture, and stirring at −78° C. was continued for 60 min. The resulting reaction mixture was treated successively with aq. sat. NH4Cl (80 ml), Et2O (250 ml) and water (75 ml). The separated 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 methyl 6-(3,5-dimethoxypyridin-4-yl)-6-(1,1-dimethylethylsulfinamido)hexanoate as a yellow oil. LC-MS (conditions A): tR=0.49 min.; [M+H]+: 387.11 g/mol.

Workup

  1. stirringstirring at −78° C.
  2. waitwas continued for 60 min
  3. customThe resulting reaction mixture
  4. washThe separated organic layer was then washed with brine (75 ml)
  5. dry with materialdried over anh. MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated to dryness under reduced pressure
  8. customPurification by FC (DCM/MeOH=25/1)

Sources & evidence

ORD record
ord-38eeb4b547b04f0d9a328cf5875ae512
Source dataset
uspto-grants-2016_01
Patent number
US09242970B2

Reaction notes

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