Reacción #346044

Ecuación de reacción

tetrahydrothiophene

aniline

sodium methoxide

tert.-butyl hypochlorite

→

aniline

2-(2-tetrahydrothienyl)aniline

Disolventes

methanol

methylene chloride

Condiciones de reacción

Tratamiento posterior

1. 1
   LavadoThe funnel was rinsed with a few ml
2. 2
   workup.ADDITIONadded dropwise to the reaction mixture
3. 3
   workup.STIRRINGstirred for three hours
4. 4
   Temperaturacooled
5. 5
   workup.ADDITIONadded quickly to the reaction mixture
6. 6
   OtroThe dry-ice/acetone cooling bath was removed
7. 7
   workup.STIRRINGthe solution stirred for 2 hours
8. 8
   OtroThe reaction was quenched by the addition of 100 ml
9. 9
   Otroof water, the heterogeneous mixture separated
10. 10
    Extracciónthe aqueous layer was extracted two times with 100-ml
11. 11
    LavadoThe combined organic layers were washed with saturated sodium chloride solution
12. 12
    Secadodried over anhydrous sodium sulfate
13. 13
    Filtraciónfiltered
14. 14
    OtroThe solvent was removed in vacuo
15. 15
    Otroto produce a dark red oil
16. 16
    workup.DISTILLATIONFractional distillation of the oil

Procedimiento

To a vigorously stirred solution of 10.0 grams (0.11 mole) of aniline in 200 ml. of methylene chloride cooled to -78° C. under nitrogen were added by means of a jacketed constant pressure additional funnel 11.7 grams (0.11 mole) of tert.-butyl hypochlorite also cooled to -78° C. This solution was stirred for 10 minutes. The funnel was rinsed with a few ml. of cold methylene chloride and 44 ml. (ca. 5 equivalents) of tetrahydrothiophene was cooled to -78° C., added dropwise to the reaction mixture, and stirred for three hours. In 50 ml. of methanol, 7.0 grams (0.13 mole, 1.2 equivalents) of sodium methoxide were placed in the funnel, cooled, and added quickly to the reaction mixture. The dry-ice/acetone cooling bath was removed and the solution stirred for 2 hours. The reaction was quenched by the addition of 100 ml. of water, the heterogeneous mixture separated, the aqueous layer was extracted two times with 100-ml. portions of methylene chloride. The combined organic layers were washed with saturated sodium chloride solution, dried over anhydrous sodium sulfate, and filtered. The solvent was removed in vacuo to produce a dark red oil. Fractional distillation of the oil gave 5.03 grams (0.054 mole) of aniline and 6.11 grams (0.034 mole) of 2-(2-tetrahydrothienyl)aniline for a 31% yield based on starting material and a 64% yield based on unrecovered starting material: b.p. 130°-134° C. (0.19 mm), ND26.8 1.6258, IR (neat) 2.92, 3.36, 6.12, 6.70, and 13.40μ, NMR (CCl4)T 7.82 (4H, m), 6.99 (2H, m) 6.06 (2H, s), 5.52 (2H, t), 3.20 (4H, m).

Fuente