氯甲酸甲酯 → Methyl 2-[[(1,1-Dimethylethyl)amino]sulfonyl]-1-methyl-1H-pyrrole-3-carboxylate

HRID 2259191

反应方程式

HRID 2259191 反应方程式
[CH3:1][C:2]([NH:5][S:6]([C:9]1[N:10]([CH3:14])[CH:11]=[CH:12][CH:13]=1)(=[O:8])=[O:7])([CH3:4])[CH3:3].C([Li])CCC.Cl[C:21]([O:23][CH3:24])=[O:22]>C1COCC1.C(OCC)(=O)C>[CH3:4][C:2]([NH:5][S:6]([C:9]1[N:10]([CH3:14])[CH:11]=[CH:12][C:13]=1[C:21]([O:23][CH3:24])=[O:22])(=[O:8])=[O:7])([CH3:1])[CH3:3]

参与物

6

反应物 3

HCID 6586氯甲酸甲酯HCID 19693810N-(1,1-Dimethylethyl)-1-methyl-1H-pyrrole-2-sulfonamideHCID 178418339正丁基锂

产物 1

HCID 19693824Methyl 2-[[(1,1-Dimethylethyl)amino]sulfonyl]-1-methyl-1H-pyrrole-3-carboxylate收率 14.3%

试剂、催化剂与溶剂 2

HCID 8028四氢呋喃溶剂2 次HCID 8857乙酸乙酯溶剂

实验过程

To a solution of 2.5 g (11.5 mmol) of N-(1,1-dimethylethyl)-1-methyl-1H-pyrrole-2-sulfonamide in 50 mL THF under nitrogen atmosphere cooled to below -70° C. was added dropwise 13 mL (32.5 mmol) of 2.5M n-butyllithium at such a rate as to keep the temperature below -58° C. After stirring at -20° C. to -10° C. for 30 min then 1 h at 0° C., the mixture was recooled to -70° C. and treated with a solution of 1.63 g (17.3 mmol) of methyl chloroformate in 6 mL THF causing an exotherm to -57° C. The reaction mixture was stirred overnight at ambient temperature then diluted with 200 mL of ethyl acetate. This solution was washed successively with two 60 mL portions of 1N HCl, brine, then dried (Na2SO4) and evaporated to a dark oil. The crude product was purified by chromatography on silica gel (30% ethyl acetate/70% hexanes) then collected from hexanes to afford 0.45 g of the title compound, m.p. 105°-108° C. 1H NMR (CDCl3, 200 MHz.) δ: 7.00 (bs,1H), 6.61 (m,2H), 3.94 (s,3H), 3.85 (s,3H), 1.21 (s,9H).

后处理

  1. customthe temperature below -58° C
  2. custom1 h
  3. customat 0° C.
  4. customwas recooled to -70° C.
  5. stirringThe reaction mixture was stirred overnight at ambient temperature
  6. washThis solution was washed successively with two 60 mL portions of 1N HCl, brine
  7. dry with materialdried (Na2SO4)
  8. customevaporated to a dark oil
  9. customThe crude product was purified by chromatography on silica gel (30% ethyl acetate/70% hexanes)
  10. customthen collected from hexanes

来源与证据

ORD记录
ord-cd81ab5f3b9144a8a083a8a98bca4ca8
来源数据集
uspto-grants-1995_12
专利号
US05472933

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