Grignard Reactions in Pyridinium and Phosphonium Ionic Liquids
0
.5 mL of a commercial 3 m ethylmagnesium bromide solution in
H, OH), 1.50 (d, J = 6.5 Hz, 3 H, CH
150 MHz): δ = 143.1 (CAr), 133.3 (CAr), 132.9 (CAr), 128.2 (CAr),
) ppm. 13C NMR (CDCl
,
3 3
Et O.
2
1
1
3
27.9 (CAr), 127.6 (CAr), 126.1 (CAr), 125.7 (CAr), 123.8 (CAr),
Reactions in Deuterated IL: These reactions were performed as per
Method B.
23.7 (CAr), 70.5 (PhCH), 25.1 (CH ) ppm. IR (neat): ν˜ = 3300,
3
–
1
053, 2971, 2924, 2878 cm .
Control Experiments: These reactions were performed exactly as
described in Method C, only in the absence of methyl iodide or the
absence of Mg turnings.
[
49]
(
1
8
؎)-1-(9-Phenanthryl)ethanol (14d): M.p. 136–138 °C, ref.
38 °C. H NMR (CDCl
3
136–
, 300 MHz): δ = 8.77–8.74 (m, 1 H, HAr),
.67–8.65 (m, 1 H, HAr), 8.17–8.14 (m, 1 H, HAr), 7.93 (br., 1 H,
1
Benzyl Alcohol (12a):[43] 1H NMR (CDCl
, 300 MHz): δ = 7.37–
.28 (m, 5 H, Ph), 4.68 (d, J = 4.9 Hz, 2 H, PhCH ), 1.98 (t, J =
, 150 MHz): δ = 140.8
Ar), 128.5 (CAr), 127.6 (CAr), 127.0 (CAr), 65.4 (CH ) ppm. MS-
O , 108.1; found, 108.1. IR (neat): ν˜ =
3
H
=
Ar), 7.91–7.88 (m, 1 H, HAr), 7.70–7.57 (m, 4 H, HAr), 5.68 (q, J
7
5
2
6.2 Hz, 1 H, ArCH), 2.05 (br., 1 H, OH), 1.73 (d, J = 6.4 Hz, 3
13
.3 Hz, 1 H, OH) ppm. C NMR (CDCl
3
13
3 3
H, CH ) ppm. C NMR (CDCl , 150 MHz): δ = 139.4 (CAr), 131.5
(
C
2
(C
(C
(C
Ar), 130.7 (CAr), 130.0 (CAr), 129.5 (CAr), 128.7 (CAr), 126.7
Ar), 126.6 (CAr), 126.6 (CAr), 126.3 (CAr), 123.8 (CAr), 123.3
+
7 8
EI (+ve) calcd. for C H
–1
3
304, 3030, 2872, 1948, 1869, 1811 cm .
Ar), 122.7 (CAr), 122.4 (CAr), 67.2 (ArCH), 24.1 (CH
3
) ppm. IR
-Biphenyl-4-methanol (12b): M.p. 98–101 °C, ref.[44] 100–101 °C. (neat): ν˜ = 3257, 2992, 2360, 2115, 1606 cm .
–1
1
1
H NMR (CDCl
3
, 300 MHz): δ = 7.62–7.59 (m, 4 H, HAr), 7.48–
.43 (m, 4 H, HAr), 7.39–7.34 (m, 1 H, HAr), 4.74 (br., 2 H, CH ),
, 150 MHz): δ = 140.8
Ar), 140.6 (CAr), 139.8 (CAr), 128.7 (CAr), 127.4 (CAr), 127.3
Benzoic Acid (17a): M.p. 119–122 °C, ref.[50] 121–123 °C. H NMR
1
7
1
2
(
[D
6
]DMSO, 400 MHz): δ = 7.96–7.93 (m, 2 H, HAr), 7.64–7.60 (m,
13
.91 (br., 1 H, OH) ppm. C NMR (CDCl
3
H, HAr), 7.52–7.48 (m, 2 H, HAr) ppm. 13C NMR ([D
1
1
1
6
]DMSO,
2
H), 132.9 (CAr), 130.9 (CAr), 129.4 (CAr),
(
(
C
C
00 MHz): δ = 167.5 (CO
Ar), 127.0 (CAr), 65.0 (CH
2
) ppm. MS-EI (+ve) calcd. for
28.6 (CAr) ppm.
+
13
C H12O , 184.1; found, 184.1. IR (neat): ν˜ = 3317, 3058, 3033,
2
–1
[51]
923, 2361 1686 cm .
4-Biphenylcarboxylic Acid (17b): M.p. 220–223 °C, ref.
224–
]DMSO, 400 MHz): δ = 8.01–8.04 (m, 2 H,
Ar), 7.79–7.82 (m, 2 H, HAr), 7.72–7.75 (m, 2 H, HAr), 7.49–7.53
1
225 °C. H NMR ([D
6
1
2
-Naphthalenemethanol (12c): M.p. 79–82 °C, ref.[45] 80–82 °C. H
H
3
NMR (CDCl , 300 MHz): δ = 7.86–7.80 (m, 4 H, HAr), 7.52–7.46
1
3
(
m, 2 H, HAr), 7.40–7.45 (m, 1 H, HAr) ppm. C NMR ([D
6
]
1
3
(
m, 3 H, HAr), 4.85 (br., 2 H, CH
2
), 1.94 (br., 1 H, OH) ppm.
C
DMSO, 100 MHz): δ = 167.2 (CO H), 144.3 (CAr), 139.0 (CAr),
1
1
2
NMR (CDCl
3
, 150 MHz) δ = 138.3 (CAr), 133.4 (CAr), 132.9 (CAr),
30.0 (CAr), 129.6 (CAr), 129.1 (CAr), 128.3 (CAr), 126.97 (CAr),
26.82 (CAr) ppm.
1
1
C
2
28.3 (CAr), 127.9 (CAr), 127.7 (CAr), 126.2 (CAr), 125.9 (CAr),
25.4 (CAr), 125.2 (CAr), 65.4 (CH ) ppm. MS-EI (+ve) calcd. for
10O , 158.1; found, 158.1. IR (neat): ν˜ = 3264, 3057, 2918,
2
+
9-Phenanthralic Acid (17d):[52] 1H NMR ([D
= 8.92–8.99 (m, 3 H, HAr), 8.59 (s, 1 H, HAr), 8.20–8.22 (m, 1 H,
Ar), 7.88 (ddd, J = 8.4, 7.0, 1.4 Hz, 1 H, HAr), 7.76–7.83 (m, 3
11
H
6
]DMSO, 400 MHz): δ
–1
853, 1917, 1601 cm .
-Phenanthrenemethanol (12d): M.p. 149–150 °C, ref.[45] 150–
H
9
1
8
1
3
1
H, HAr) ppm. C NMR ([D
H), 131.6 (CAr), 131.4 (CAr), 130.3 (CAr), 130.0 (CAr), 129.8 (CAr),
29.2 (CAr), 128.6 (CAr), 127.5 (CAr), 127.2 (CAr), 127.0 (CAr),
6 2
]DMSO, 100 MHz): δ = 168.8 (CO
52 °C. H NMR (CDCl
3
, 300 MHz): δ = 8.76–8.73 (m, 1 H, HAr),
.69–8.66 (m, 1 H, HAr), 8.18–8.15 (m, 1 H, HAr), 7.90–7.87 (m, 1
1
H, HAr), 7.80 (br., 1 H, HAr), 7.72–7.57 (m, 4 H, HAr), 5.20 (d, J
3
126.4 (CAr), 123.4 (CAr), 123.0 (CAr) ppm.
=
5.4 Hz, 2 H, CH
2
) 1.85 (t, J = 5.9 Hz, 1 H, OH) ppm. 1 C NMR
(
(
(
(
CDCl , 150 MHz): δ = 134.5 (CAr), 131.4 (CAr), 130.7 (CAr), 130.4
3
Supporting Information (see footnote on the first page of this arti-
cle): H, C and P NMR spectra of the ILs and reaction prod-
ucts.
1
13
31
C
C
C
Ar), 130.1 (CAr), 128.6 (CAr), 126.8 (CAr), 126.8 (CAr), 126.8
Ar), 126.6 (CAr), 125.9 (CAr), 124.2 (CAr), 123.2 (CAr), 122.5
+
Ar), 64.0 (CH
2
) ppm. MS-EI (+ve) calcd. for C15
H
12O , 208.1;
–
1
found, 208.1. IR (neat): ν˜ = 3169, 2871, 2362, 2342, 1608 cm .
؎)-1-Phenyl-1-propanol (13a):[42] 1H NMR (CDCl
, 300 MHz): δ
7.39–7.26 (m, 5 H, Ph), 4.60 (t, J = 6.6 Hz, 1 H, PhCH), 2.07
br., 1 H, OH), 1.89–1.72 (m, 2 H, CH ), 0.93 (t, J = 7.4 Hz, 3 H,
Acknowledgments
(
=
(
3
The authors thank the ARC Centre for Free Radical Chemistry
and Biotechnology for financial support.
2
3
CH ) ppm.
(
؎)-1-Phenylethanol (14a):[46] 1H NMR (CDCl
3
, 300 MHz): δ =
.39–7.29 (m, 5 H, Ph), 4.88 (q, J = 6.5 Hz, 1 H, PhCH), 2.10 (br.,
H, OH), 1.58 (d, J = 6.5 Hz, 3 H, CH
) ppm. 13C NMR (CDCl
50 MHz): δ = 145.8 (CAr), 128.4 (CAr), 127.4 (CAr), 125.3 (CAr),
0.3 (CH), 25.1 (CH ) ppm. IR (neat): ν˜ = 3341, 2973, 1947, 1880,
[
[
1] M. J. Earle, K. R. Seddon, Pure Appl. Chem. 2000, 72, 1391–
398.
2] a) K. R. Seddon, Nat. Mater. 2003, 2, 363–365; b) N. V. Plech-
kova, K. R. Seddon, Chem. Soc. Rev. 2008, 37, 123–150; c) M.
Maase, in: Ionic Liquids in Synthesis (Eds.: P. Wasserscheid, T.
Welton), Wiley-VCH, Weinheim, 2008, vol. 2, pp. 663–687.
7
1
1
7
1
1
3
3
,
3
–
1
808 cm .
؎)-1-(4-Biphenyl)ethanol (14b): M.p. 93–96 °C, ref.[47] 94–96 °C.
[3] a) M. Zhang, V. Kamavaram, R. G. Reddy, Miner. Metall. Pro-
cess. 2006, 23, 177–186; b) P. U. Naik, G. McManus, M. J. Za-
worotko, R. D. Singer, Dalton Trans. 2008, 4834–4836; c) J. R.
Harjani, P. U. Naik, T. Fri sˇ cˇ i c´ , L. R. MacGillivray, R. D.
Singer, Dalton Trans. 2008, 4595–4601.
[4] a) Y. Ogomi, T. Kato, S. Hayase, J. Photopolym. Sci. Technol.
2006, 19, 403–408; b) M. Gorlov, L. Kloo, Dalton Trans. 2008,
2655–2666.
(
1
H NMR (CDCl
3
, 300 MHz): δ = 7.61–7.58 (m, 4 H, HAr), 7.47–
.43 (m, 4 H, HAr), 7.38–7.34 (m, 1 H, HAr), 4.96 (q, J = 6.4 Hz,
H, ArCH), 1.99 (br., 1 H, OH), 1.55 (d, J = 6.4 Hz, 3 H, CH
7
1
3
)
13
ppm. C NMR (CDCl
40.4 (CAr), 128.7 (CAr), 127.2 (CAr), 127.0 (CAr), 125.8 (CAr), 70.1
CH), 25.1 (CH ) ppm. IR (neat): ν˜ = 3296, 3065, 3034, 2361, 2343
3
, 150 MHz): δ = 144.8 (CAr), 140.8 (CAr),
1
(
3
–
1
[5] a) Z. Li, J. Chang, H. Shan, J. Pan, Rev. Anal. Chem. 2007, 26,
cm .
1
09–153; b) R. D. Singer, P. J. Scammells, Tetrahedron Lett.
(
؎)-1-(2-Naphthyl)ethanol (14c): M.p. 69–72 °C, ref.[48] 72–74 °C.
2
001, 42, 6831–6833; c) I. Hemeon, N. W. Barnett, N. Gath-
1
H NMR (CDCl
3
, 300 MHz): δ = 7.85–7.80 (m, 4 H, HAr), 7.52–
ergood, P. J. Scammells, R. D. Singer, Aust. J. Chem. 2004, 57,
7.47 (m, 3 H, HAr), 5.06 (q, J = 6.4 Hz, 1 H, ArCH), 2.13 (br., 1
125–128.
Eur. J. Org. Chem. 2011, 942–950
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
949