10.1002/ejoc.201901445
European Journal of Organic Chemistry
FULL PAPER
(C5H5+, 51), 39 (C3H3+, 15). HRMS (ASAP, AI+) M+ m/z 201.0530; calc. for
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General procedure: β-trifluoromethyl vinyl sulfide synthesis. The thiol (1
equivalent) was dissolved in anhydrous DMSO under an argon atmosphere
then NaHMDS (2M in THF, 2 equivalents) was added dropwise and the
resulting mixture stirred at room temperature for 30 minutes. The reaction
mixture was stirred under an atmosphere of 1 (excess) provided via gas
bladder for 3 hours then carefully quenched, filtered and subjected to aqueous
workup as for the enol ethers described above to give the crude product
without further purification unless otherwise specified.
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(E)-1-(4-(tert-Butyl)benzyl)thio-3,3,3-trifluoroprop-1-ene (4a). Following the
general procedure, 4-(tert-butyl)benzyl mercaptan (0.498 g, 2.75 mmol), 1
(1.65 g, 14.5 mmol) and NaHMDS (2.5 mL, 5.0 mmol) in anhydrous DMSO (15
mL) gave (E)-1-(4-(tert-butyl)benzyl)thio-3,3,3-trifluoroprop-1-ene, 4a (0.688 g,
91%) as a yellow oil. δH (400 MHz; CDCl3) 1.36 (9H, s, tBu), 3.97 (2H, s, CH2),
16
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2
3
2
4
5.57 (1H, dq, JHH 11.0, JHF 8.5, C(2)H), 6.69 (1H, dq, JHH 11.0, JHF 1.0,
18
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C(1)H), 7.29 (2H, m, ArH), 7.41 (2H, m, ArH). δF (376 MHz; CDCl3) −59.88 (dd,
4
2
3JHF 8.5, JHF 1.0). δC (101 MHz; CDCl3) 31.42, 34.69, 60.54, 112.88 (q, JCF
35.0, C2), 123.60 (q, 1JCF 270.9, CF3), 125.95, 128.79, 133.45, 138.72 (q, 3JCF
5.1, C1), 150.92. IR max /cm−1 2963, 1737, 1615, 1516, 1464, 1364, 1268,
1203, 1111, 1047, 1018. GC-MS (EI+) m/z 274 (M+, 17%), 147 (100,
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i
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Acknowledgments
We are grateful to GlaxoSmithKline and EPSRC for the award of
an iCASE studentship to B.J.M. and Durham University MChem
programme for funding to E.D.B.; we also thank Dr. Dmitri S.
Yufit for X-ray crystallography analysis.
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Keywords: fluorine • organofluorine compounds • trifluoromethyl
• HFO-1234yf • enol ethers
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