K. Okuma et al.
Bull. Chem. Soc. Jpn., 78, No. 10 (2005) 1833
ꢁ
1
1
35.00 (Ar). Anal. Found: C, 64.82; H, 4.81%. Calcd for
0
mp 220–222 C). H NMR (CDCl3) ꢁ 1.62 (m, 1H, CHH), 2.35
(m, 1H, CHH), 2.71 (m, 1H, CHH), 3.28 (m, 1H, CHH), 6.80
(m, 1H, Ar), 6.92–7.05 (m, 2H, Ar), 7.19 (m, 1H, Ar), 7.24 (m,
1H, P-CH), 7.62 (m, 6H, Ph), 7.73 (m, 3H, Ph), 7.86 (m, 6H,
Ph). 13C NMR (CDCl3) ꢁ 27.23 (CH2), 31.12 (CH2), 39.47 (d,
JPC ¼ 43 Hz, CH), 118.43 (d, JPC ¼ 83 Hz, ipso-PPh3), 125.32,
126.86, 127.18, 129.24, 130.40, 134.23, 134.44, 134.90, 146.32.
Similarly, 1,2,3,4-tetrahydro-1-naphthyltriphenylphosphonium
bromide (2i) was obtained in 69% yield. 2i: Colorless crystals,
C26H23BrClP: C, 64.49; H, 4.84%. 2e : Colorless crystals, mp
ꢁ
1
2
53–254 C. H NMR (CDCl3) ꢁ 1.79 (dd, 3H, J ¼ 6:8 Hz, JHP ¼
1
9:6 Hz, CH3), 2.21 (s, 3H, CH3), 6.67 (dq, 1H, J ¼ 6:8 Hz,
JHP ¼ 13:6 Hz, CH), 6.95 (d, 2H, J ¼ 8:0 Hz, Ar), 7.03 (d, 2H,
1
3
J ¼ 8:0 Hz, Ar), 7.55–7.86 (m, 15H, Ph). C NMR (CDCl3)
ꢁ 17.38 (CH3), 21.38 (TolCH3), 34.80 (d, JPC ¼ 42 Hz, CH),
117.99 (d, JPC ¼ 82 Hz, ipso-PPh3), 129.65, 130.32, 130.43,
134.86, 135.01, 138.93. Anal. Found: C, 70.29; H, 5.68%. Calcd
ꢁ
1
for C27H26BrP: C, 70.18; H, 5.64%.
mp 256–258 C. H NMR (CDCl3) ꢁ 1.29–1.38 (m, 1H, CHH),
1.48–1.64 (m, 2H, CH2), 1.95–2.12 (m, 1H, CH2), 2.38 (brd,
1H, J ¼ 15:6 Hz, CHH), 2.87–3.02 (m, 1H, CHH), 6.81–7.14
Reaction of Allylbenzene with Triphenylphosphonium Fluo-
roborate. After a mixture of triphenylphosphine (0.52 g, 2.0
mmol) and aq HBr (48%, 0.30 g, 1.8 mmol) was heated at 110
13
(m, 5H, Ar þ CH), 7.57–7.92 (PPh3). C NMR (CDCl3) ꢁ
21.35 (d, JPC ¼ 5 Hz, CH2), 24.73, 29.08, 34.49 (d, JPC ¼ 42
Hz, CH2), 118.68 (d, JPC ¼ 82 Hz, ipso-PPh3), 126.40 (d, JPC ¼
4 Hz, Ar), 126.99 (d, JPC ¼ 7 Hz, Ar), 128.25 (d, JPC ¼ 4 Hz,
Ar), 129.58 (d, JPC ¼ 4 Hz, Ar), 130.33 (d, JPC ¼ 12 Hz, PPh3),
131.21 (d, JPC ¼ 5 Hz, Ar), 134.68 (d, JPC ¼ 9 Hz, PPh3),
134.75 (PPh3), 141.82 (d, JPC ¼ 5 Hz, Ar). Elemental analysis
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C for 30 min, then allylbenzene (0.21 g, 1.8 mmol) was added.
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The reaction mixture was heated at 160 C for 1 h and cooled
to rt. The resulting mixture was dissolved into acetone (10 mL)
and added to a solution of sodium tetraphenylborate (0.34 g, 1.0
mmol) in acetone (10 mL). Colorless crystals of triphenylphos-
phonium tetraphenylborate immediately precipitated, which were
filtered and the filtrate was evaporated to give a pale-brown solid.
Methanol (10 mL) was added to this solid to afford colorless crys-
tals, which were recrystallized from acetone to afford colorless
crystals of (1-phenylpropyl)triphenylphosphonium tetraphenyl-
borate (0.26 g, 0.36 mmol). 2f: Colorless crystals, mp 207–208
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was carried out on its tetrafluoroborate. mp 235–236 C. Anal.
Found: C, 69.89; H, 5.58%. Calcd for C28H26BF4P: C, 70.02;
H, 5.46%.
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1
References
C. H NMR (CD3SOCD3) ꢁ 0.83 (t, 3H, J ¼ 6:8 Hz, Me),
1
1
7
6
.90–2.05 (m, 1H, CHH), 2.18–2.27 (m, 1H, CHH), 5.27 (brt,
H, J ¼ 13:0 Hz, CH), 6.70–7.20 (m, 22H, o-Ph þ BPh4), 7.25–
.40 (m, 3H, Ph), 7.53–7.90 (PPh3). Anal. Found: C, 87.29; H,
.75%. Calcd for C51H46BP: C, 87.42; H, 6.62%.
1
G. Wittig and G. Geissler, Liebigs Ann. Chem., 580, 44
(1953); For a review, see: H. Pommer, Angew. Chem., Int. Ed.
Engl., 16, 423 (1977).
2 For a review: ‘‘The Chemistry of Organophosphorus
Compounds,’’ Vol. 3.
Reaction of Stilbene 1g with Triphenylphosphonium Fluo-
roborate. A mixture of triphenylphosphine (0.52 g, 2.0 mmol),
aq HBF4 (48%, 0.44 mL, 2.0 mmol), and 1g (0.49 g, 2.0 mmol)
was heated in microwave oven (600 W) for 3 min. The obtained
colorless solid was recrystallized from ethanol to give colorless
crystals of (1,2-diphenylethyl)triphenylphosphonium tetrafluoro-
borate (0.56 g, 1.05 mmol). 1g: Colorless crystals. mp 211–213
3
S. Yamamoto, K. Okuma, and H. Ohta, Bull. Chem. Soc.
Jpn., 61, 4476 (1988); K. Okuma, Y. Tanaka, H. Ohta, and H.
Matsuyama, Heterocycles, 36, 37 (1993); K. Okuma, Y. Tanaka,
H. Ohta, and H. Matsuyama, Bull. Chem. Soc. Jpn., 66, 2623
(1993).
4
K. Okuma, S. Maekawa, S. Shibata, K. Shioji, T. Inoue, T.
ꢁ
1
C. H NMR (CDCl3) ꢁ 3.26 (dt, 1H, J ¼ 5:2, 8.0 Hz, PhCHH),
Kurisaki, H. Wakita, and Y. Yokomori, Eur. J. Org. Chem., 2003,
3727; K. Okuma, K. Kubo, and Y. Yokomori, Heterocycles, 60,
299 (2003); K. Okuma, K. Kojima, and S. Shibata, Heterocycles,
52, 2753 (2000).
3
.64 (brdd, 1H, J ¼ 8:0, 12.4 Hz, PhCHH), 5.11 (brt, 1H, J ¼
:0 Hz, CH), 6.80–7.30 (m, 10H, Ph), 7.57–7.87 (m, 15H, PPh3).
C NMR (CDCl3) ꢁ 37.16 (CH2), 44.41 (d, JPC ¼ 43 Hz, CH),
17.00 (d, JPC ¼ 82 Hz, ipso-PPh3), 127.37, 128.90, 129.07,
29.38, 129.60, 130.58, 130.79, 130.96, 134.64, 135.73, 135.87.
8
13
1
1
5
E. E. Schweizer and A. T. Wehman, J. Chem. Soc. C, 1971,
343; W. G. Dauben, J. M. Gerdes, and R. A. Bunce, J. Org.
Chem., 49, 4293 (1984).
Anal. Found: C, 72.47; H, 5.32%. Calcd for C32H28BF4P: C,
7
2.22; H, 5.34%.
Reaction of Indene 1h with Triphenylphosphonium
6 H. J. Bestmann, R. Harl, and H. Haberlein, Liebigs Ann.
Chem., 718, 33 (1968).
Bromide. A mixture of triphenylphosphine (0.79 g, 3.0 mmol)
ꢁ
7
E. Reimann and E. Hargasser, Arch. Pharm., 322, 159 (1989).
8 M. Arisawa and M. Yamaguchi, J. Am. Chem. Soc., 122,
2387 (2000).
9 W. G. Dauben, J. M. Gerdes, and R. A. Bruce, J. Org.
Chem., 49, 4293 (1984).
R. Sato and K. Chino, Tetrahedron Lett., 32, 6345 (1991);
and aq HBr (48%, 0.45 g, 2.7 mmol) was heated to 110 C for
0 min, and then indene 1h (0.31 g, 2.7 mmol) was added. The
3
ꢁ
reaction mixture was heated to 160 C for 1 h and cooled to rt.
The obtained colorless solid was recrystallized from ethanol to
give colorless crystals of 1-indanyltriphenylphosphonium bromide
(
0.75 g, 1.94 mmol). 2h: Colorless crystals, mp 221–222 C (lit.6
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