반응 #923

반응 방정식

sulfur dioxide

n-butyllithium

N-methyl-pyrrole

t-butylamine

→

title compound

수율 28.5%

N-(1,1-Dimethylethyl)-1-methyl-1H-pyrrole-2-sulfonamide

수율 28.5%

용매

THF

반응 조건

후처리

1. 1
   기타the temperature below -60° C
2. 2
   workup.ADDITIONwas added rapidly
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   기타at -20° C.
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   workup.STIRRINGAfter stirring for 1 h at ambient temperature
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   기타the THF was removed under reduced pressure
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   기타The solids were triturated with ether
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   여과collected by filtration with an ether
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   세척rinse
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   기타then dried under nitrogen
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    workup.ADDITIONThis intermediate sulfinate salt was added to a well
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    workup.STIRRINGstirred
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    workup.ADDITIONmixture of 350 mL water and 250 mL dichloromethane
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    온도chilled to 0° C
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    workup.ADDITIONN-Chlorosuccinimide was then added in portions so as
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    기타the temperature below 3° C
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    workup.STIRRINGThe mixture was stirred vigorously for 30 min at ambient temperature
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    기타after which time, the layers were separated
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    세척the organic layer was washed successively with 10% aq NaHSO3, twice with aq NaHCO3
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    건조dried (MgSO4)
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    여과filtered
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    온도This dichloromethane solution was then cooled to 0° C.
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    workup.ADDITIONwas added over 2 min
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    workup.STIRRINGAfter stirring for 1 h at ambient temperature
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    기타solids had precipitated from the brown solution which
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    workup.WAITwas then left
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    workup.STIRRINGstirring for 3 days
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    workup.ADDITIONThe mixture was diluted with more dichloromethane
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    세척then washed three times with 1N HCl
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    건조once with saturated aq NaCl, dried (MgSO4)
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    기타evaporated
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    기타The resulting solid residue was triturated
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    기타collected with a mixture of hexanes and n-chlorobutane

실험 절차

A solution of 10 g (0.12 mol) of N-methyl-pyrrole in 120 mL of anhydrous THF under nitrogen atmosphere was cooled to below -70° C. then treated with 56 mL of 2.4M n-butyllithium in hexanes (0.13 mol) dropwise at such a rate as to keep the temperature below -60° C. The resulting brown colored mixture was stirred for 16 h at ambient temperature, then recooled to below -70° C. at which time liquified sulfur dioxide (9.0 mL, 0.21 mol) was added rapidly, causing an exotherm at -20° C. and the formation of a thick golden colored precipitate. After stirring for 1 h at ambient temperature, the THF was removed under reduced pressure. The solids were triturated with ether and collected by filtration with an ether rinse then dried under nitrogen. This intermediate sulfinate salt was added to a well stirred mixture of 350 mL water and 250 mL dichloromethane chilled to 0° C. N-Chlorosuccinimide was then added in portions so as to keep the temperature below 3° C. The mixture was stirred vigorously for 30 min at ambient temperature, after which time, the layers were separated and the organic layer was washed successively with 10% aq NaHSO3, twice with aq NaHCO3, dried (MgSO4) and filtered. This dichloromethane solution was then cooled to 0° C. and stirred while 82 mL (0.30 mol) of t-butylamine was added over 2 min. After stirring for 1 h at ambient temperature, solids had precipitated from the brown solution which was then left stirring for 3 days. The mixture was diluted with more dichloromethane then washed three times with 1N HCl, once with saturated aq NaCl, dried (MgSO4) and evaporated. The resulting solid residue was triturated and collected with a mixture of hexanes and n-chlorobutane to afford 7.4 g of the title compound as tan crystals, m.p. 125°-126° C.

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