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Chevykalova et al.
was dried at 0.01 Torr to give compound 1 (13.06 g, 89%) as
pale yellow crystals, m.p. 6364 °C (cf. Ref. 3: m.p. 80 °C).
1H NMR (C6D6), δ: 2.12.18, 2.42.6, 2.682.78 (all m,
4 H, CH2 of P ring); 3.2 (AB, 2 H, CH2 of Cp ring, 2J = 40 Hz);
6.97.4 (m, 9 H, Ar). 31P NMR (C6D6), δ: 13.1 (s). 13C NMR
5a from salt 8 (12.78 g, 0.049 mol) in CH2Cl2 (60 mL).
Compound 5b is a pale yellow crystalline substance, yield 0.72 g
(7.2%), m.p. 114 °C. H NMR (CDCl3), δ: 1.7 (d, 3 H, Ìå,
1
J = 13.2 Hz); 2.462.54, 2.82.92, 3.043.16 (all m, 4 H,
CH2 of P ring); 3.49 (AB, 2 H, CH2 of Cp ring, 2J = 22.85 Hz);
7.317.53 (m, 4 H, Ar). 31P NMR (CDCl3),, δ: 48.07 (s).
2
(CDCl3), δ: 26.79 (d, CH2, J = 5.0 Hz); 31.16 (br.s, CH2);
1
1
36.67 (d, CH2P, JPC = 15.7 Hz); 119.88, 124.17, 125.15,
13C NMR (CDCl3), δ: 17.62 (d, CH3, JPC = 71 Hz); 22.85
1
127.78 (C(4)C(7)); 128.37 (d, Cm, Cm´
,
3JPC = 7.0 Hz);
(CH2); 30.44 (d, CH2P, JPC = 72.5 Hz); 34.37 (d, CH2,
128.97 (br.s, Cp); 132.12 (d, Co, Co´, 2JPC = 18.7 Hz); 133.86
(d, JPC = 10.9 Hz); 139.8 (d, JPC = 17 Hz); 141.33, 150.0
(d, JPC = 8 Hz); 150.1 (d, JPC = 4.2 Hz), Ci, C(3a), C(3b),
C(7a), C(8a). Found (%): C, 81.54; H, 6.06. C17H15P. Calcu-
lated (%): C, 81.58; H, 6.04.
2JPC = 10.85 Hz); 120.76, 124.82, 126.71, 127.47 (C(4)C(7));
139.2, 140.2, 149.4 (d, JPC = 7.5 Hz); 164.4 (d, JPC = 35.1 Hz),
C(3a), C(3b), C(7a), C(8a). Found (%): C, 70.56; H, 6.43;
O, 7.82. C12H13OP. Calculated (%): C, 70.58; H, 6.42; O, 7.83.
1-Phenyl-2,3-dihydro-8H,1λ5-indeno[2,1-b]phosphole-1-
thione (6a). Sulfur (0.79 g, 0.024 mol) was added to a solution
of compound 1 (5 g, 0.02 mol) in CH2Cl2 (100 mL). the
reaction mixture was stirred for 2 h and then filtered. The
filtrate was concentrated at a reduced pressure to give com-
pound 6a (5.5 g, 97.5%) as a thick oil. 1H NMR (C6D6),
δ: 3.94.2 (m, 4 H, CH2 of P ring); 4.68 (AB, 2 H, CH2 of
1-Methyl-2,3-dihydro-8H-indeno[2,1-b]phosphole (3).
Compound 3 was synthesized as described for compound 1
(except that stirring was continued for 3 days) from salt 8
(10.38 g, 0.04 mol) and LiAlH4 (1.52 g, 0.04 mol) in Et2O
(50 mL). The product was a yellow oil, yield 6.05 g (80.4%).
1H NMR (CDCl3),, δ: 1.23 (d, 3 H, Me, J = 2.2 Hz);
2.162.24, 2.582.72, 2.822.94, 3.033.18 (all m, 4 H, CH2
of P ring); 3.43 (AB, 2 H, CH2 of Cp ring, 2J = 3.4 Hz); 7.24
(td, 1 H); 7.297.37 (m, 2 H); 7.5 (d, 1 H) (ÀÂCD, Ar).
31P NMR (CDCl3), δ: 32.74 (s). 13C NMR (CDCl3), δ: 13.8
2
Cp ring, J = 22.7 Hz); 8.579.45 (m, 9 H, Ar). 31P NMR
(C6D6), δ: 46.88 (s). 13C NMR (C6D6), δ: 24.43 (CH2); 33.72
2
1
(d, CH2, JPC = 11.3 Hz); 39.29 (d, CH2P, JPC = 59.2 Hz);
120.97, 125.13, 126.79, 127.31 (C(4)C(7)); 128.6 (d, Co,
1
2
2
(d, CH3, JPC = 20.7 Hz); 26.36 (d, CH2, JPC = 5.9 Hz);
Co´, JPC = 12.3 Hz); 131.14 (Cp); 131.23 (d, Cm, Cm´
,
2
1
29.86 (d, CH2, JPC = 8.8 Hz); 36.11 (d, CH2P, JPC
=
3JPC = 4.1 Hz); 135.19 (d, JPC = 77.4 Hz); 140.35, 141.24,
150.14 (d, 2JPC = 7.9 Hz); 163.64 (d, JPC = 31.9 Hz) Ci, C(3a),
C(3b), C(7a), C(8a). Found (%): C, 72.30; H, 5.36; S, 11.38.
C17H15PS. Calculated (%): C, 72.32; H, 5.35; S, 11.36.
16.0 Hz); 119.3, 123.8, 124.3, 126.1 (C(4)C(7)); 141.64 (d,
JPC = 3.8 Hz); 149.4 (d, JPC = 14.7 Hz); 149.64 (d,
JPC = 3.8 Hz); 155.9 (d, JPC = 6.0 Hz), (C(3a), C(3b), C(7a),
C(8a). Found (%): C, 76.61; H, 6.94. C12H13P. Calculated (%):
C, 76.58; H, 6.96.
1-Methyl-1,2,3,8-tetrahydro-1λ5-indeno[2,1-b]phosphole-
1-thione (6b). The compound was synthesized as described for
compound 6a from phosphole 3 (2 g, 0.011 mol) in CH2Cl2
(100 mL) and sulfur (0.42 g, 0.013 mol). The product is a thick
4,7-Dimethyl-1-phenyl-2,3-dihydro-8H-indeno[2,1-b]phos-
phole (4). Compound 4 was synthesized as described for com-
pound 1 from salt 9 (3.21 g, 9.2 mmol) and LiAlH4 (0.35 g,
9.2 mmol) in Et2O (50 mL). Compound 4 is a rose oil, yield
1.67 g (65.23%). 1H NMR (C6D6), δ: 2.04, 2.32 (both s,
each 3 H, C(4)Ìå, C(7)Ìå); 2.42.8 (m, 4 H, CH2 of P ring);
3.04 (AB, 2 H, CH2 of Cp ring, 2J = 8 Hz); 6.86, 6.96
(both d, 2 H, Ar, J = 8 Hz); 7.077.1, 7.127.16, 7.437.48
(all m, 5 H, Ph). 31P NMR (C6D6), δ: 18.76 (s). Found (%):
C, 81.94; H, 6.91. C19H19P. Calculated (%): C, 81.99; H, 6.88.
1-Phenyl-2,3-dihydro-8H,1λ5-indeno[2,1-b]phosphol-1-one
(5à). A 10% aqueous solution of KHCO3 (20 mL) was added to
a solution of compound 2 (0.77 g, 0.0024 mol) in CH2Cl2
(30 mL). The reaction mixture was stirred for 1 h. The products
were extracted with CH2Cl2 (3½20 mL), and the combined
organic phases were washed with water and dried over MgSO4.
The solvent was removed at a reduced pressure, and the residue
was recrystallized from heptane to give compound 5a (0.05 g,
7.8%) as yellow crystals, m.p. 162 °C. 1H NMR (CDCl3),
δ: 2.62.76, 2.963.08, 3.183.28 (all m, 4 H, CH2 of P ring);
1
oil. Yield 2.2 g (94%). H NMR (CDCl3), δ: 2.05 (d, 3 H,
Ìå, J = 13.2 Hz); 2.712.83, 2.872.96, 2.973.08,
3.143.24 (all m, 4 H, CH2 of P ring); 3.61 (AB, 2 H, CH2 of
2
Cp ring, J = 22.8 Hz); 7.357.56 (m, 4 H, Ar). 31P NMR
(CDCl3), δ: 45.88 (s). 13C NMR (CDCl3), δ: 23.48 (d, CH3,
1JPC = 54.2 Hz); 24.25 (CH2); 33.75 (d, CH2, 2JPC = 11.6 Hz);
1
36.89 (d, CH2P, JPC = 58.1 Hz); 120.78, 124.81, 126.76,
127.28 (C(4)C(7)); 139.68, 140.53, 149.3 (d, J = 7.7 Hz);
161.92 (d, JPC = 32.2 Hz), C(3a), C(3b), C(7a), C(8a).
Found (%): C, 65.45; H, 5.94; S, 14.53. C12H13PS. Calcu-
lated (%): C, 65.43; H, 5.95; S, 14.55.
References
1. F. Mathey and J.-P. Lampin, Tetrahedron, 1975, 31, 2685.
2. A. Fallis, K. Anderson, and P. Rath, Organometallics, 1992,
11, 885.
3. D. Quin, N. Hughes, H. Lawson, and L. Good, Tetrahedron,
1983, 39, 401.
4. R. Bergamasco and N. Porter, Aust. J. Chem., 1977, 30, 1051.
5. A. Weisberger, E. Proskauer, J. Riddick, and E. Toops,
Technique of Organic Chemistry, New York, 1955, vol. 7.
6. H. Norman, Bull. Soc. Chim., France, 1957, 5, 728.
7. R. T. Hart and R. F. Tebbe, J. Am. Chem. Soc., 1950,
72, 3286.
2
3.5 (AB, 2 H, CH2 of Cp ring, J = 22.8 Hz); 7.37.7 (m,
9 H, Ar). 31P NMR (CDCl3),, δ: 44.84 (s). 13C NMR
2
(CDCl3), δ: 23.24 (d, CH2, JPC = 2.7 Hz); 31.75 (d, CH2P,
1JPC = 74.1 Hz); 34.43 (d, CH2, 2J = 10.6 Hz); 120.9, 124.92
4
4
(d, JPC = 1.5 Hz); 126.75 (d, JPC = 1.5 Hz); 127.66
(C(4)C(7)); 128.58 (d, Co, Co´, 2JPC = 12.2 Hz); 130.45 (d,
3
4
Cm, Cm´, JPC = 10.6 Hz); 131.59 (d, CP, JPC = 2.9 Hz);
133.76 (d, J = 101.1 Hz); 138.39, 140.02, 149.99 (d,
JPC = 8 Hz); 166.95 (d, JPC = 35.6 Hz), Ci, C(3a), C(3b),
C(7a), C(8a). Found (%): C, 76.71; H, 5.67; O, 6.02. C17H15OP.
Calculated (%): C, 76.68; H, 5.68; O, 6.01.
1-Methyl-2,3-dihydro-8H,1λ5-indeno[2,1-b]phosphol-1-one
(5b). Compound 5b was synthesized as described for compound
Received July 20, 2000;
in revised form October 12, 2000