2023_BG_2A_1 - Thiourea formation on 3-fluoroaniline

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Reaction scheme

Outcome

2.5425 g (quantitative)

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1. Dissolved KSCN (1.17g, 10.8 mmol, 1.2 equiv.) in acetone (50 mL)
2. Added benzoyl chloride (1.15 mL, 9.9 mmol, 1.1 equiv.)
3. Heated to 60 C and stirred for 20 minutes
4. Added 3-fluoroaniline (1.00 g, 9 mmol)
5. Stirred at 60 C for 25 minutes

TLC indicated completion.

20% ethyl acetate in hexanes, ninhydrin stain

Rf values

0.51, 0.69, 0.87.

6. Poured over ~ 150 mL ice water to precipitate out
7. Vacuum filtered
8. Washed with cold water (2 x 15 mL) and cold isopropanol (2 x 15 mL) to yield a fluffy pale yellow solid

Empty vial: 15.9753 g Full vial: 15.9763 g Mass: 2.5425 g

9. Left in dessicator overnight

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LRMS

297.09 [M+Na]+, 273.02 [M-H]-

2023_BG_2A_1.pdf 2023_BG_2A_1.d.zip

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H NMR

1H NMR (300 MHz, CDCl3) δ 9.07 (s, 1H), 7.91 7.89 (d, 2H), 7.77 - 7.74 (dt, 1H), 7.67 (t, 2H), 7.56 (t, 2H), 7.43 - 7.33 (m, 2H), 6.99 (tt, 1H).

2023_BG_2A_1.pdf 2023_BG_2A_1_1.zip

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500 MHz NMR

1H NMR (500 MHz, DMSO-d6) δ 12.69 (s, 1H), 11.65 (s, 1H), 8.03 – 7.97 (m, 2H), 7.86 – 7.80 (m, 1H), 7.72 – 7.63 (m, 1H), 7.60 – 7.51 (m, 2H), 7.53 – 7.43 (m, 2H), 7.13 (ddt, J = 10.7, 6.5, 2.3 Hz, 1H).

19F NMR (471 MHz, DMSO) δ -112.11.

13C NMR (126 MHz, DMSO) δ 179.22, 168.23, 162.64, 160.71, 139.64 (d), 133.17, 132.06, 130.28 (d), 128.70, 128.44, 120.23, 112.94 (d), 111.13 (d), 30.66.

2023_BG_2A 500 MHz.pdf 230709_2A_1.zip 230709_2A_2.zip 230709_2A_3.zip