1,2-Dichloroethane → 1-(Chloromethyl)-4-(methylthio)benzene

Temperature

-5 °C

A solution of 24.8 g. (0.20 mole) of thioanisole in 180 ml. of ethylene dichloride was cooled to -5°C in an ice-methanol bath. 48 Ml. (83.6 g., 0.44 mole) of titanium tetrachloride was added dropwise over 15 minutes while maintaining the temperature at 0°-5°C. Another 10 ml. of ethylene dichloride was employed to wash forward the last quantities of titanium tetrachloride. The solution was cooled to -5°C again and 16.8 g. (0.22 mole) of methylal was added over 15 minutes while holding the temperature at 0-5°C. The reaction was stirred for 24 hours at 0-5°C and was quenched in 250 g. of ice. The organic layer was separated and the aqueous layer was extracted with 2 × 100 ml. of ethylene dichloride. The combined organic layers were dried over anhydrous magnesium sulfate and concentrated in vacuo at 50°-60°C to give 31.6 g. of crude product. Quantitative vpc analysis showed the product to contain a 64% yield of p-methylthiobenzyl chloride and a 5% yield of the ortho isomer.

1. temperaturewhile maintaining the temperature at 0°-5°C
2. washto wash forward the last quantities of titanium tetrachloride
3. customat 0-5°C
4. customwas quenched in 250 g
5. customThe organic layer was separated
6. extractionthe aqueous layer was extracted with 2 × 100 ml
7. dry with materialThe combined organic layers were dried over anhydrous magnesium sulfate
8. concentrationconcentrated in vacuo at 50°-60°C
9. customto give 31.6 g

ORD record

ord-670848beffbd47159d543f2839e01e95

Source dataset

uspto-grants-1976_04

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US03953520