E
E. Voutyritsa et al.
Special Topic
Synthesis
4-Bromododecanenitrile (2a)
Yield: 27 mg (28%) (under an Ar atmosphere); yellow oil; 80:20 mix-
ture of diastereomers.
Yield: 211 mg (90%); yellow oil.
1H NMR (200 MHz, CDCl3): δ = 4.18 (dd, J = 7.3, 1.8 Hz, 0.80 H, CHBr),
3.81–3.73 (m, 0.20 H, CHBr), 2.61–2.26 (m, 3 H, CNCH2 and CH), 2.19–
2.05 (m, 1 H, CH), 1.89–1.77 (m, 1 H, CH), 1.70–1.43 (m, 3 H, 3 × CHH),
1.39–1.17 (m, 3 H, 3 × CHH).
13C NMR (50 MHz, CDCl3): δ = 119.6, 58.6, 57.3, 49.7, 48.1, 44.5, 44.2,
42.1, 41.2, 34.7, 33.1, 29.6, 29.1, 27.2, 23.8, 23.1, 21.3.
1H NMR (200 MHz, CDCl3): δ = 4.13–3.95 (m, 1 H, CHBr), 2.60 (t, J =
6.9 Hz, 2 H, NCCH2), 2.22–1.98 (m, 2 H, CH2), 1.90–1.73 (m, 2 H, CH2),
1.61–1.39 (m, 2 H, CH2), 1.37–1.12 (m, 10 H, 5 × CH2), 0.87 (t, J = 6.2
Hz, 3 H, CH3).
13C NMR (50 MHz, CDCl3): δ = 118.8, 55.0, 38.8, 34.5, 31.7, 29.3, 29.1,
28.8, 27.4, 22.6, 16.0, 14.0.
HRMS (ESI): m/z [M + H]+ calcd for C9H13BrN: 214.0226; found:
214.0231.
HRMS (ESI): m/z [M + H]+ calcd for C12H23BrN: 260.1008; found:
260.1013.
4-Bromo-5-(2-cyclohexylethoxy)pentanenitrile (2g)
4-Bromooctanenitrile (2b)
Yield: 94 mg (65%); orange oil.
Yield: 74 mg (72% yield); yellow oil.
1H NMR (200 MHz, CDCl3): δ = 4.20–4.05 (m, 1 H, CHBr), 3.72 (dd, J =
10.5, 5.0 Hz, 1 H, OCHH), 3.64–3.36 (m, 3 H, OCH2 and OCHH), 2.68–
2.51 (m, 2 H, NCCH2), 2.45–2.27 (m, 1 H, CHH), 2.16–1.95 (m, 1 H,
CHH), 1.77–1.57 (m, 4 H, CH and 3 × CHH), 1.51–1.34 (m, 3 H,
3 × CHH), 1.27–1.10 (m, 3 H, 3 × CHH), 1.03–0.75 (m, 3 H, 3 × CHH).
13C NMR (50 MHz, CDCl3): δ = 118.7, 74.1, 69.5, 49.9, 36.9, 34.5, 33.3,
31.2, 26.5, 26.2, 15.7.
1H NMR (200 MHz, CDCl3): δ = 4.15–3.96 (m, 1 H, CHBr), 2.61 (t, J =
6.7 Hz, 2 H, NCCH2), 2.23–1.99 (m, 2 H, CH2), 1.93–1.75 (m, 2 H, CH2),
1.60–1.22 (m, 4 H, 2 × CH2), 0.92 (t, J = 7.0 Hz, 3 H, CH3).
13C NMR (50 MHz, CDCl3): δ = 118.8, 55.0, 38.6, 34.5, 29.5, 22.0, 16.0,
13.9.
HRMS (ESI): m/z [M + H]+ calcd for C8H15BrN: 204.0382; found:
204.0389.
HRMS (ESI): m/z [M + H]+ calcd for C13H23BrNO: 288.0958; found:
288.0964.
4-Bromo-5-cyclopentylpentanenitrile (2c)
Yield: 67 mg (57%); brown oil.
4-Bromo-7-hydroxyheptanenitrile (2h)
Reaction with 20 mol% of the catalyst.
Yield: 31 mg (30%); yellow oil.
1H NMR (200 MHz, CDCl3): δ = 4.15–3.96 (m, 1 H, CHBr), 2.62 (t, J =
6.7 Hz, 2 H, NCCH2), 2.22–1.95 (m, 3 H, CH2 and CH), 1.92–1.70 (m, 3
H, 3 × CHH), 1.68–1.41 (m, 5 H, 5 × CHH), 1.19–0.95 (m, 2 H, 2 × CHH).
1H NMR (200 MHz, CDCl3): δ = 4.20–4.05 (m, 1 H, CHBr), 3.70 (t, J =
6.0 Hz, 2 H, OCH2), 2.62 (t, J = 6.0 Hz, 2 H, NCCH2), 2.20–1.60 (m, 6 H,
3 × CH2).
13C NMR (50 MHz, CDCl3): δ = 119.1, 62.1, 55.0, 35.5, 34.9, 30.7, 16.3.
HRMS (ESI): m/z [M + Na]+ calcd for C7H12BrNONa: 227.9994; found:
13C NMR (50 MHz, CDCl3): δ = 118.8, 54.4, 45.2, 38.1, 34.7, 32.5, 31.8,
24.9, 24.8, 15.9.
HRMS (ESI): m/z [M + H]+ calcd for C10H17BrN: 230.0539; found:
230.0542.
227.9994.
4-Bromo-4-cyclohexylbutanenitrile (2d)
Yield: 107 mg (93%); yellow oil.
4-Bromo-6-cyanohexyl 4-Methylbenzenesulfonate (2i)
Reaction with 20 mol% of the catalyst.
1H NMR (200 MHz, CD3OD): δ = 4.09–3.92 (m, 1 H, CHBr), 2.72–2.52
(m, 2 H, NCCH2), 2.19–2.02 (m, 2 H, CH2), 1.88–1.47 (m, 6 H, CH and
5 × CHH), 1.36–1.04 (m, 5 H, 5 × CHH).
Yield: 105 mg (58%); orange oil.
13C NMR (50 MHz, CD3OD): δ = 118.8, 62.0, 44.4, 31.8, 30.6, 29.3, 26.0,
25.9, 25.8, 16.4.
HRMS (ESI): m/z [M + H]+ calcd for C10H17BrN: 230.0539; found:
230.0546.
1H NMR (200 MHz, CDCl3): δ = 7.79 (d, J = 8.8 Hz, 2 H, ArH), 7.36 (d, J =
8.8 Hz, 2 H, ArH), 4.06 (t, J = 6.0 Hz, 2 H, OCH2), 4.00–3.90 (m, 1 H,
CHBr), 2.59 (t, J = 7.0 Hz, 2 H, NCCH2), 2.45 (s, 3 H, CH3), 2.15–1.78 (m,
6 H, 3 × CH2).
13C NMR (50 MHz, CDCl3): δ = 145.3, 132.9, 130.2, 128.1, 118.8, 69.6,
53.9, 35.0, 34.8, 27.3, 22.0, 16.3.
2-(2-Bromocyclooctyl)acetonitrile (2e)
Reaction with 20 mol% of the catalyst.
HRMS (ESI): m/z [M + Na]+ calcd for C14H18BrNO3SNa: 382.0083;
found: 382.0086.
Yield: 46 mg (58%) (under an Ar atmosphere); pale yellow oil; 77:23
mixture of diastereomers.
4-Bromo-5-hydroxyhexanenitrile (2j)
1H NMR (200 MHz, CDCl3): δ = 4.51–4.26 (m, 0.77 H, CHBr), 4.22–4.08
(m, 0.23 H, CHBr), 2.40–2.17 (m, 3 H, CNCH2 and CH), 2.15–1.19 (m,
12 H, 6 × CH2).
Reaction with 20 mol% of the catalyst.
Yield: 48 mg (50%); brown oil; 1:1 mixture of diastereomers.
13C NMR (50 MHz, CDCl3): δ = 118.93, 118.87, 56.2, 55.8, 35.6, 35.5,
35.1, 34.3, 33.7, 32.8, 30.3, 30.2, 30.1, 29.4, 25.8, 25.5, 25.4, 24.9, 24.6,
24.2.
HRMS (ESI): m/z [M + H]+ calcd for C10H17BrN: 230.0539; found:
230.0544.
1H NMR (200 MHz, CDCl3): δ = 4.17–4.02 (m, 1 H, CHBr), 4.00–3.89
(m, 1 H, OCH), 3.77 (br s, 1 H, OH), 2.70–2.53 (m, 2 H, NCCH2), 2.29–
2.13 (m, 2 H, CH2), 1.34 (d, J = 6.3 Hz, 1.5 H, CH3), 1.31 (d, J = 6.3 Hz,
1.5 H, CH3).
13C NMR (50 MHz, CDCl3): δ = 118.7, 70.3, 69.8, 61.9, 61.0, 31.0, 29.2,
21.3, 19.8, 16.1, 16.0.
HRMS (ESI): m/z [M + H]+ calcd for C6H11BrNO: 192.0019; found:
trans-2-(3-Bromobicyclo[2.2.1]heptan-2-yl)acetonitrile (2f)
Reaction with 20 mol% of the catalyst.
192.0020.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–G