Dimethylformamide → HCID 145857610, compound

HRID 723111Notes

Reaction equation

HRID 723111 reaction equation
C([Mg]Cl)(C)C.[C:6]([O:10][C:11](=[O:32])[NH:12][C:13]([C:15]1[S:16][C:17]([S:30][CH3:31])=[C:18]([S:20]([C:23]2[CH:28]=[CH:27][CH:26]=[C:25](Br)[CH:24]=2)(=[O:22])=[O:21])[CH:19]=1)=[NH:14])([CH3:9])([CH3:8])[CH3:7].[Li]CCCC.CN(C)[CH:40]=[O:41]>C1COCC1>[C:6]([O:10][C:11](=[O:32])[NH:12][C:13]([C:15]1[S:16][C:17]([S:30][CH3:31])=[C:18]([S:20]([C:23]2[CH:28]=[CH:27][CH:26]=[C:25]([CH:40]=[O:41])[CH:24]=2)(=[O:22])=[O:21])[CH:19]=1)=[NH:14])([CH3:9])([CH3:8])[CH3:7]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 145857672tert-butyl N-[4-(3-bromophenyl)sulfonyl-5-methylsulfanylthiophene-2-carboximidoyl]carbamateHCID 178418339ButyllithiumHCID 178418918HCID 178418918, compound

Product 1

HCID 145857610HCID 145857610, compoundYield 75%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

A solution of 2 M i-PrMgCl in THF (1.1 mL, 2.2 mmol) was added dropwise at 0° C. to {[4-(3-bromo-benzenesulfonyl)-5-methylsulfanyl-thiophen-2-yl]-imino-methyl}-carbamic acid tert-butyl ester (0.5 g, 1.0 mmol) (Example 27c) in 5.0 mL THF. The solution was stirred for 20 mins at 0° C., then cooled to −78° C. and a solution of 2.5 M n-BuLi in hexanes (0.6 mL, 1.5 mmol) was added. The mixture was stirred for 5 mins then N,N-dimethylformamide (0.30 mL, 3.8 mmol) was added at −78° C. and the mixture allowed to attain RT. The reaction was quenched with sat. NH4Cl (10 mL) and extracted with EtOAc (3×20 mL), dried over Na2SO4 and evaporated. The crude solid was purified by elution from a 20 g SPE with 50% EtOAc/hex to give 0.33 g (75%) of the title compound as a yellow solid: 1H NMR (400 MHz, CDCl3) δ 10.06 (s, 1H), 8.48 (s, 1H), 8.26 (m, 1H), 8.10 (m, 1H), 8.06 (s, 1H), 7.71 (s, 1H), 2.50 (s, 3H), 1.51 (s, 9H). Mass spectrum (ESI, m/z) calcd. for C18H20N2O5S3 440.1, found 440.8 (M+H).

Workup

  1. temperaturecooled to −78° C.
  2. stirringThe mixture was stirred for 5 mins
  3. customto attain RT
  4. customThe reaction was quenched with sat. NH4Cl (10 mL)
  5. extractionextracted with EtOAc (3×20 mL)
  6. dry with materialdried over Na2SO4
  7. customevaporated
  8. customThe crude solid was purified by elution from a 20 g SPE with 50% EtOAc/hex

Sources & evidence

ORD record
ord-1df2c1c808f24660926f39dda591e5e1
Source dataset
uspto-grants-2006_11
Patent number
US07138530B2

Reaction notes

Loading…