Ruthenium-Catalyzed Synthesis of 1,5-Dichlorides
115.90–116.34 (m, aromatic), 119.70, 119.74, 119.86 (CN), 128.58–
136.12 (m, aromatic), 161.55–164.16 (m, C-F). C18H15Cl2F2N
(354.23): calcd. C 61.03, H 4.27, N 3.95; found C 61.05, H 4.33, N
4.01.
2,2-Bis(2-chloro-2-phenylethyl)malononitrile (7): Flash chromatog-
raphy on silica gel: hexane/ethyl acetate, 88:12. The product (1.51 g,
88%) was obtained as a mixture of 2 diastereoisomers (ratio from
GC: A:B = 1.0:1.1). 1H NMR (CDCl3, 400 MHz): δ = 2.60–2.83
(m, CH2, 8 H, A, B), 5.15–5.21 (m, CHCl, 4 H, A, B), 7.35–7.50
(m, aromatic, 20 H, A, B). 13C NMR (CDCl3, 100 MHz): δ = 34.08
[C(CN)2], 47.12, 47.19 (CH2), 57.83, 57.88 (CHCl), 112.49, 113.23,
114.05 (CN), 127.24 (br), 129.28 (br), 129.82 (br), 138.45 (aro-
matic). C19H16Cl2N2 (343.26): calcd. C 66.48, H 4.70, N 8.16;
found C 66.36, H 4.78, N 8.17.
2,2-Bis[2-chloro-2-(naphthalen-2-yl)ethyl]malononitrile (8): Flash
chromatography on silica gel: hexane/ethyl acetate, 88:12. The
product (2.00 g, 90%) was obtained as a mixture of 2 diastereoiso-
mers (ratio from GC: A:B = 1.0:1.0). 1H NMR (CDCl3, 400 MHz):
δ = 2.64–2.94 (m, CH2, 8 H, A, B), 5.33–5.38 (m, CHCl, 4 H, A, B),
7.43–7.57 (m, aromatic, 6 H, A, 6 H, B), 7.77–7.90 (m, aromatic, 8
H, A, 8 H, B). 13C NMR (CDCl3, 100 MHz): δ; 34.23 [C(CN)2],
46.76, 46.86 (CH2), 58.26, 58.35 (CHCl), 112.66, 113.44, 114.23
(CN), 123.80, 123.84, 126.86, 126.91, 127.01, 127.22, 127.86,
128.26, 128.28, 129.58, 129.59, 132.91, 133.66, 135.52, 135.60 (aro-
matic). C27H20Cl2N2 (443.38): calcd. C 73.14, H 4.55, N 6.32;
found C 72.84, H 4.54, N 6.29.
4-Chloro-2-(2-chloro-2-phenylethyl)-4-phenylbutanenitrile (4): Flash
chromatography on silica gel: hexane/ethyl acetate, 9:1. The prod-
uct (1.45 g, 91%) was obtained as a mixture of 3 diastereoisomers
1
1
(ratio from H NMR: δ = A:B:C = 1.0:1.0:1.8). H NMR (CDCl3,
400 MHz): δ = 2.19–2.41 (m, CH2, 7 H, A, B, 3 H, C), 2.47–2.62
(m, CH2, 1 H, A or B, 1 H, C, CHCN, 1 H, A or B), 2.87–2.97
(m, CHCN, 1 H, C), 3.52–3.62 (m, CHCN, 1 H, A or B), 4.99–
5.15 (m, CHCl, 6 H, A, B, C), 7.25–7.39 (m, aromatic, 30 H, A, B,
C). 13C NMR (CDCl3, 100 MHz): δ = 27.33, 27.99, 28.71 (CHCN),
41.10, 41.89, 41.94, 42.41 (CH2), 59.33, 59.36, 60.58, 60.80 (CHCl),
119.92, 120.02, 120.09 (CN), 126.81, 126.83 (br), 126.94 (br),
127.01, 129.04 (br), 129.12, 129.21 (br), 129.28, 139.10, 139.21,
140.091, 140.24 (aromatic) ppm. C18H17Cl2N (318.25): calcd. C
67.93, H 5.38, N 4.40; found C 68.05, H 5.32, N 4.46.
Ethyl 4-Chloro-2-(2-chloro-2-phenylethyl)-2-cyano-4-phenylbutano-
ate (9): Flash chromatography on silica gel: hexane/ethyl acetate,
85:15. The product (1.77 g, 90%), was obtained as a mixture of 3
diastereoisomers (ratio from 1H NMR A:B:C = 1.0:2.0:3.0). 1H
NMR (CDCl3, 400 MHz): δ = 0.87, (t, J = 7.2 Hz, CH3, 3 H, B),
1.16 (dd, J = 7.2, 7.2 Hz, CH3, 3 H, C), 1.43 (t, J = 7.2 Hz, CH3,
3 H, A), 2.26–2.31 (m, CH2, 2 H, A), 2.43–2.47 (m, CH2, 1 H, B),
2.52–2.57 (m, CH2, 1 H, B), 2.67–2.72 (m, CH2, 2 H, B), 2.84–3.00
(m, CH2, 2 H, A, 4 H, C, OCH2, 2 H, B), 3.57–3.84 (m, OCH2, 2
H, C), 4.36 (q, J = 7.2 Hz, OCH2, 2 H, A), 5.08–5.18 (m, CHCl, 6
H, A, B, C), 7.24–7.45 (m, aromatic, 30 H, A, B, C). 13C NMR
(CDCl3, 100 MHz): δ = 13.17, 13.53, 13.82 (CH3), 46.86 (CH2),
46.97 (CCN), 47.09 (CH2), 47.31 (CCN), 47.51 (CH2), 47.55
(CCN), 47.82 (CH2), 58.49, 58.62, 58.93, 58.96 (CHCl), 62.93,
63.26, 63.66 (OCH2), 116.93, 117.11, 117.21 (CN), 126.92, 127.8,
127.89, 128.60, 128.69, 128.99, 129.03, 129.11, 129.14, 129.18,
129.21, 138.6, 138.7, 140.2 (aromatic), 166.26, 167.06, 167.79 (CO-
4-Chloro-2-[2-chloro-2-(4-chlorophenyl)ethyl]-4-(4-chlorophenyl)-
butanenitrile (5): Flash chromatography on silica gel: hexane/ethyl
acetate, 9:1. The product (1.75 g, 90%) was obtained as a mixture
of 3 diastereoisomers (ratio from 1H NMR A:B:C = 1.0:1.7:2.3).
1H NMR (CDCl3, 400 MHz): δ = 2.19–2.40 (m, CH2, 3 H, A, 4 H,
B, 3 H, C), 2.43–2.59 (m, CH2, 1 H, A, 1 H, C, CHCN, 1 H, A),
2.85–2.94 (m, CHCN, 1 H, C), 3.50–3.58 (m, CHCN, 1 H, B), 4.93–
5.09 (m, CHCl, 6 H, A, B, C), 7.25–7.41 (m, aromatic, 24 H, A, B,
C) ppm. 13C NMR (CDCl3, 100 MHz): δ = 27.20, 27.91, 28.63
(CHCN), 40.89, 41.77, 41.86, 42.35 (CH2), 58.30, 58.36, 59.63,
59.84 (CHCl), 119.63, 119.67, 119.78 (CN), 128.16, 128.18, 128.31,
128.37, 129.23 (br), 129.35, 129.44, 134.87, 134.89, 135.14, 135.15,
137.51, 136.64, 138.50, 138.66 (aromatic) ppm. C18H15Cl4N
(387.14): calcd. C 55.84, H 3.91, N 3.62; found C 55.76, H 3.94, N
3.57.
OEt). IR (film): ν = 1737 (C=O) cm–1. C H Cl NO (390.31):
˜
21 21
2
2
calcd. C 64.92, H 5.42, N 3.59; found C 65.03, H 5.70, N 3.58.
Diethyl 2,2-Bis(2-chloro-2-phenylethyl)malonate (10): Flash
chromatography on silica gel: hexane/ethyl acetate, 9:1. The prod-
uct (1.23 g, 70%) was obtained as a mixture of 2 diastereoisomers
(ratio from 1H NMR: A:B = 1.0:1.4). 1H NMR (CDCl3, 400 MHz):
δ = 1.14 (t, J = 7.1 Hz, CH3, 3 H, B), 1.18 (dd, J = 7.1, 7.1 Hz,
CH3, 6 H, A), 1.28 (t, J = 7.1 Hz, CH3, 3 H, B), 2.83–3.05 (m,
CH2, 8 H, A, B), 3.84–4.03 (m, OCH2, 4 H, A, 2 H, B), 4.16 (q, J
= 7.14 Hz, OCH2, 2 H, B), 4.86–4.90 (m, CHCl, 2 H, A), 4.97–
5.00 (m, CHCl, 2 H, B), 7.29–7.41 (m, aromatic, 20 H, A, B). 13C
NMR (CDCl3, 100 MHz): δ = 13.58, 13.79, 13.82, 13.92 (CH3),
42.03, 42.19 (CH2), 55.72, 55.74 [C(CO2Et)2], 58.86, 59.07 (CHCl),
61.64, 61.83, 61.91 (OCH2), 127.06, 127.16, 128.65, 128.71, 128.75,
128.76, 141.39, 141.56 (aromatic), 169.54, 169.81, 170.40 (COOEt).
4-Chloro-2-[2-chloro-2-(4-fluorophenyl)ethyl]-4-(4-fluorophenyl)-
butanenitrile (6): Flash chromatography on silica gel: hexane/ethyl
acetate, 9:1. The product (1.31 g, 92%)was obtained as a mixture
1
of 3 diastereoisomers (ratio from H NMR: A:B:C = 1.0:1.7:2.3).
1H NMR (CDCl3, 400 MHz): δ = 2.17–2.37 (m, CH2, 3 H, A, 4 H,
B, 3 H, C), 2.44–2.60 (m, CH2, 1 H, A, 1 H, C, CHCN, 1 H, A),
2.85–2.94 (m, CHCN 1 H, C), 3.48–3.59 (m, CHCN, 1 H, B), 4.96–
5.07 (m, CHCl, 6 H, A, B, C), 7.25–7.41 (m, aromatic, 24 H, A, B,
IR (film): ν = 1728 (C=O) cm–1. C H Cl O (437.36): calcd. C
˜
23 26
2
4
63.16, H 5.99; found C 63.37, H 6.47.
C). 13C NMR (CDCl3, 100 MHz): δ = 27.24, 27.97, 28.69 (CHCN), 2-(1-Chloro-2,3-dihydro-1H-indan-2-yl)-2-(2-chloro-2-phenylethyl)-
41.06, 41.95, 42.02, 42.49 (CH2), 58.39, 58.45, 59.75, 59.93 (CHCl), malononitrile (11): Flash chromatography on silica gel: hexane/ethyl
Eur. J. Org. Chem. 2011, 249–255
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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