Potassium Hydroxide → 2-Cyclopropylmethylthio-pyrrole

A solution of 2-thiocyanopyrrole (12.4 g., 0.1 mole) and cyclopropylmethyl bromide (14.85 g., 0.11 mole) in methanol (500 ml.) was cooled below 0° (ice-salt bath), and stirred vigorously under nitrogen while a solution of potassium hydroxide (12.3 g., 0.22 mole) in 1:1 (by volume) aqueous methanol (400 ml.) was added dropwise during 0.75 hours. The cooling bath was removed and stirring continued for 1.5 hours before neutralization of the excess alkali with solid carbon dioxide. The reaction mixture was poured into 20% brine (500 ml.) and extracted with methylene chloride (3×100 ml.). The combined organic extracts were dried (Na2SO4 +K2CO3), then evaporated in vacuo to provide a red oil (12.1 g.). Distillation of this crude oil afforded 2-cyclopropylmethylthio-pyrrole as a colorless oil (5.8 g. 38%), B.P. 138°-141° at 11 mm. (B) The product from Part A was reacted with ethyl oxalyl chloride as described in Example 39, Part B. Chromatography on silica followed by recrystallization from petroleum ether (B.P. 40°-60°) and hexane gave 5-cyclopropylmethylthio-2-pyrrolylglyoxylic acid ethyl ester as a yellow solid, M.P. 46°. Found: C, 56.81; H, 6.23; N, 5.38. C12H15NO3S requires: C, 56.89; H, 5.97; N, 5.53%.

1. additionwas added dropwise during 0.75 hours
2. customThe cooling bath was removed
3. additionThe reaction mixture was poured into 20% brine (500 ml.)
4. extractionextracted with methylene chloride (3×100 ml.)
5. dry with materialThe combined organic extracts were dried (Na2SO4 +K2CO3)
6. customevaporated in vacuo
7. customto provide a red oil (12.1 g.)
8. distillationDistillation of this crude oil

ORD record

ord-20bb4eac9fc84a49a6d086acb2907e05

Source dataset

uspto-grants-1981_01

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US04243672