反応 #346044

反応方程式

tetrahydrothiophene

aniline

sodium methoxide

tert.-butyl hypochlorite

→

aniline

2-(2-tetrahydrothienyl)aniline

溶媒

methanol

methylene chloride

反応条件

後処理

1. 1
   洗浄The 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
   温度cooled
5. 5
   workup.ADDITIONadded quickly to the reaction mixture
6. 6
   その他The dry-ice/acetone cooling bath was removed
7. 7
   workup.STIRRINGthe solution stirred for 2 hours
8. 8
   その他The reaction was quenched by the addition of 100 ml
9. 9
   その他of water, the heterogeneous mixture separated
10. 10
    抽出the aqueous layer was extracted two times with 100-ml
11. 11
    洗浄The combined organic layers were washed with saturated sodium chloride solution
12. 12
    乾燥dried over anhydrous sodium sulfate
13. 13
    ろ過filtered
14. 14
    その他The solvent was removed in vacuo
15. 15
    その他to produce a dark red oil
16. 16
    workup.DISTILLATIONFractional distillation of the oil

実験手順

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).

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