Nishiyama et al.
261
1
28.2, 128.3, 129.4, 129.5, 139.1, 144.6, 144.7; MS m/z (rel.
128.3, 128.9, 139.1; MS m/z (rel. intensity): 207(8), 107(25),
intensity): 163(12), 119(42), 105(13), 91(100), 77(10).
92(12), 91(100), 73(17), 65(17). Anal. calcd. for C H 0 :
2
0
26 2
C 85.06, H 9.28; found; C 85.11, H 9.19.
Bis(2-hexyl) ether (2e) (16b)
1
H NMR δ: 0.89 (t, J = 7.0 Hz, 3H), 1.10 (t, J = 6.2 Hz,
Pentyl 2-phenyl-1-propyl ether (3d)
–
1
3
1
H), 1.09 (d, J = 5.9 Hz, 3H), 1.11 (d, J = 6.2 Hz, 3H),
.21–1.38 (m, 10H), 1.45–1.49 (m, 2H), 3.39–3.42 (m, 2H);
C NMR δ: 14.1, 20.5, 21.1, 22.8, 22.9, 27.9, 28.1, 36.9,
7.3, 72.9, 73.4; MS m/z (rel. intensity): 152(10), 137(20),
29(17), 85(100), 69(11), 57(17).
IR (neat, cm ): 2945, 2850, 1721, 1595, 1491, 1445,
1
1388, 1105, 755, 696; H NMR δ: 0.88 (t, J = 7.3 Hz, 3H),
1
3
1.29 (d, J = 6.9 Hz, 3H), 1.25–1.30 (m, 4H), 1.53–1.55 (m,
2H), 2.98–3.02 (m, 1H), 3.38–3.45 (m, 3H), 3.53 (dd, J =
3
1
1
3
9.3, 6.1Hz, 1H), 7.18–7.31 (m, 5H); C NMR δ: 14.1, 18.4,
2.5, 28.4, 29.4, 71.2, 126.3, 127.4, 128.3, 144.7; MS m/z
2
+
Bis(3-phenyl-2-propyl) ether (2f)
(rel. intensity): 206 (M , 8), 120(17), 106(12), 105(100),
104(36), 91(50), 79(16), 78(12), 77(23), 71(80), 69(13),
43(32). Anal. calcd. for C H O: C 81.49, H 10.75; found:
–
1
IR (neat, cm ): 2960, 2920, 1599, 1495, 1450, 1370,
1
1
(
(
122, 749, 709; H NMR δ: 0.98 (d, J = 5.9 Hz, 3H), 1.10
d, J = 5.9 Hz, 3H), 2.50 (dd, J = 6.6, 13.2 Hz, 1H), 2.60
dd, J = 6.6, 13.2 Hz, 1H), 2.74 (dd, J = 6.2, 13.2 Hz, 1H),
1
4
22
C 81.20, H 10.45.
2
7
7
.84 (dd, J = 6.2, 13.2 Hz, 1H), 3.54–3.62 (m, 2H), 7.08–
.27 (m, 10H); C NMR δ: 20.2, 20.7, 43.8, 43.9, 74.9,
5.4, 126.0, 128.1, 128.2, 129.5, 129.6, 139.3; MS m/z (rel.
Pentyl 1-phenylethyl ether (3e)
1
3
–1
IR (neat, cm ): 2910, 2850, 1600, 1492, 1451, 1370,
1
1105, 760, 703; H NMR δ: 0.88 (t, J = 7.3 Hz, 3H), 1.28–
intensity): 163(24), 119(51), 92(9), 91(100), 65(9). Anal.
calcd. for C H O: C 84.99, H 8.72; found: C 84.87, H
8
1.34 (m, 4H), 1.42 (d, J = 6.6 Hz, 3H), 1.55–1.56 (m, 2H),
4.37 (q, J = 6.6 Hz, 1H), 3.28 (t, J = 6.6 Hz, 2H), 7.23–7.35
1
8
22
1
3
.97.
(m, 5H); C NMR δ: 14.0, 22.6, 24.3, 28.4, 29.5, 29.7, 68.8,
26.1, 127.3; MS m/z (rel. intensity): 121(13), 104(24),
1
General procedure for the synthesis of unsymmetrical
ethers
Unsymmetrical ethers were prepared using triflates in place
105(100), 91(10), 79(18), 77(34). Anal. calcd. for C13H20O:
C 81.19, H 10.48; found: C 81.13, H 10.26.
of Tf O. To a solution of magnesium di(benzyl alcoholate),
generated in situ from 1a (2.16 g, 0.02 mol), magnesium
1-(3-Phenyl-2-propoxy) pentane (3f)
2
–
1
IR (neat, cm ): 2920, 2810, 1719, 1590, 1485, 1442,
1
(
0.24 g, 0.01 mol), and iodine (50 mg, 0.2 mmol) in benzyl
1365, 1101, 735, 693; H NMR δ: 0.88 (t, J = 7.3 Hz, 3H),
alcohol (2.16 g, 0.02 mol) was added dropwise a solution of
pentyl triflate (2.2 g, 0.01 mol) in 5 mL of dry ether. The
mixture was stirred at room temperature for 1 h, the reaction
was quenched by the addition of water. After the usual
work-up, chromatography of the residue with hexane/ethyl
acetate (80/20) afforded benzyl pentyl ether 3a (1.55 g,
1.27–1.31 (m, 7H), 1.53–1.55 (m, 2H), 2.98–3.01 (m, 1H),
3.38–3.44 (m, 3H), 3.52–3.55 (m, 1H), 7.18–7.31 (m, 5H);
1
3
C NMR δ: 14.1, 19.6, 22.5, 28.4, 29.8, 43.2, 68.8, 76.7,
+
126.0, 128.2, 129.5, 139.3; MS m/z (rel. intensity): 206 (M ,
4), 115(95), 97(14), 92(28), 91(100), 77(10), 72(18), 71(98),
65(21), 55(16), 45(93), 43(99). Anal. calcd. for C H O: C
1
4
22
8
7%).
81.49, H 10.75; found: C 81.12, H 11.01.
Benzyl pentyl ether (3a) (17)
1-(2-Methyl-3-phenyl-2-propoxy) pentane (3g)
1
–1
H NMR δ: 0.89 (t, J = 7.0 Hz, 3H), 1.29–1.35 (m, 4H),
IR (neat, cm ): 2906, 2850, 1595, 1490, 1448, 1375,
1
1
7
7
.57–1.64 (m, 2H), 3.46 (t, J = 6.6 Hz, 2H), 4.50 (s, 2H),
.25–7.34 (m, 5H); C NMR δ: 14.1, 22.5, 28.4, 29.5, 36.4,
1.1, 71.8, 126.1, 128.3, 128.9, 139.1; MS m/z (rel. inten-
1359, 1222, 1145, 1122, 1080, 725, 698; H NMR δ: 0.91 (t,
1
3
J = 6.9 Hz, 3H), 1.12 (s, 6H), 1.32–1.35 (m, 6H), 2.77 (s,
2H), 3.39 (t, J = 6.6 Hz, 2H), 7.19–7.25 (m, 5H); C NMR
δ: 14.1, 25.2, 28.6, 30.3, 47.1, 61.4, 71.0, 74.9, 125.9, 127.8,
1
3
sity): 92(61), 91(100), 77(9), 65(15).
1
30.6, 138.7; MS m/z (rel. intensity): 135(7), 130(8),
Pentyl phenetyl ether (3b)
129(82), 117(8), 92(11), 91(53), 71(14), 65(10), 60(10),
59(100), 55(10), 43(34). Anal. calcd. for C H O: C 81.76,
H 10.98; found: C 82.02, H 11.01.
–
1
IR (neat, cm ): 2910, 2840, 1598, 1492, 1449, 1360,
1
5
24
1
1
110, 743, 695; H NMR δ: 0.89 (t, J = 7.3 Hz, 3H), 1.28–
1
.32 (m, 4H), 1.55–1.59 (m, 2H), 2.87 (t, J = 6.9 Hz, 2H),
.42 (t, J = 6.9 Hz, 2H), 3.63 (t, J = 6.9 Hz, 2H), 7.17–7.29
3
1
3
(
m, 5H); C NMR δ: 14.1, 22.5, 28.4, 29.5, 36.4, 71.1, 71.9,
+
1. H.H. Freedman and R.A. Dubois. Tetrahedron Lett. 38, 3251
1975).
1
1
9
6
8
26.1, 128.3, 128.9, 139.1; MS m/z (rel. intensity): 192 (M ,
9), 174(8), 106(38), 105(44), 104(17), 103(18), 101(11),
2(24), 91(54), 79(21), 78(16), 77(28), 71(100), 69(18),
5(17), 55(9), 51(9), 43(63). Anal. calcd for C H O: C
(
2
3
. M. Yamashita and Y. Takegami. Synthesis, 803 (1977).
. J. March. In Advanced organic chemistry, reactions, mecha-
nisms, and structure. 2nd ed. McGraw–Hill Book Company,
New York. 1978. pp. 357–358.
1
3
20
1.19, H 10.48; found: C 81.01, H 10. 35.
4
5
6
. S. Torii, S. Takagishi, T. Inokuchi, and H. Okumoto. Bull.
Chem. Soc. Jpn. 60, 775 (1987).
. F.M. Callahan, G.W. Anderson, R. Paul, and J.E. Zimmerman.
J. Am. Chem. Soc. 85, 201 (1963).
. F. Toda, H. Takumi, and M. Akehi. J. Chem. Soc. Chem.
Commun. 1270 (1990).
Bis(phenethoxy) butane (3c)
–
1
IR (neat, cm ): 2920, 2845, 1732, 1598, 1595, 1450,
1
1
364, 1109, 749, 699; H NMR δ: 1.60–1.62 (m, 4H), 2.87
(
7
t, J = 7.0 Hz, 4H), 3.46 (t, J = 7.0 Hz, 4H), 3.61 (t, J =
.0 Hz, 4H); C NMR δ: 26.5, 36.4, 70.7, 71.8, 126.1,
1
3
©
1999 NRC Canada