3-Thiophenethiol → (-)-3-((2-Amino-2-ethylhexyl)thio)thiophene

HRID 398826Notes

Reaction equation

HRID 398826 reaction equation
[S:1]1[CH:5]=[CH:4][C:3]([SH:6])=[CH:2]1.[CH2:7]([C:11]1([CH2:14][CH3:15])[CH2:13][NH:12]1)[CH2:8][CH2:9][CH3:10]>>[NH2:12][C:11]([CH2:14][CH3:15])([CH2:7][CH2:8][CH2:9][CH3:10])[CH2:13][S:6][C:3]1[CH:4]=[CH:5][S:1][CH:2]=1

Participants

3

Reactant 2

HCID 822023-ThiophenethiolHCID 217099702-Butyl-2-ethylaziridine

Product 1

HCID 18968871(-)-3-((2-Amino-2-ethylhexyl)thio)thiopheneYield 78.3%

Procedure

To a solution of n-butyl lithium in hexane (194 ml 1.6M) under nitrogen at -78° C. was added diethyl ether(120 ml) and then dropwise 3-bromothiophene (28 ml). The reaction was warmed to -30° C. and then cooled to -50° C. and powdered sulfur (10 g) was added. The reaction was stirred 15 hours at room temperature and then a solution of potassium hydroxide (24 g) in 160 ml water was added and the ether layer was discarded. The aqueous layer was treated at -5° C. with 6N hydrochloric acid (125 ml) and extracted with dichloromethane and the extract was dried over magnesium sulfate. Filtration and solvent removal afforded crude 3-thiophenthiol (14.1 g). The crude 3-thiophenthiol (10 g) was combined with 2-butyl-2-ethylaziridine (12.6 g, Synthetic Example 1(f)) at 0° C. and the reaction was stirred 15 hours at room temperature. The crude reaction product was purified by column chromatography on silica using 5% methanol in diethyl ether as eluant to give the desired product as an oil (16.4 g). 1H NMR is consistent with proposed structure.

Workup

  1. customThe crude reaction product
  2. customwas purified by column chromatography on silica using 5% methanol in diethyl ether as eluant

Sources & evidence

ORD record
ord-81e63bab68a6482999520579b3e32836
Source dataset
uspto-grants-1998_10
Patent number
US05817652

Reaction notes

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