Synthesis and Spectral Characterization of Benzoxazaphosphinin N-Substituted Amines by the Staudinger Reaction 503
TABLE 2 1H NMR Chemical Shifts of 5–12
Compound
Ar–H
N–CH2
Hydrogens of R
5
6
6.44–6.91 (m, 12H) 4.09 (s, 2H) 1.43–1.62 (m, 2H, –CH2–CH3), 0.92 (t, 3H, J = 11.6 Hz, CH2–CH3)
6.17–6.97 (m, 12H) 4.07 (s, 2H) 1.62–1.86 [m, CH(CH3)CH2CH3], 0.98 [d, 3H, J = 8.6 Hz,
CH(CH3)CH2CH3], 1.24–1.37 [m, 2H, CH(CH3)CH2CH3], 0.89 [t, 3H,
J = 8.2 Hz, CH(CH3)CH2CH3]
7
6.66–6.97 (m. 12H) 4.21 (s, 2H) 1.15–1.32 (m, 2H, –CH2 CH2–CH3), 1.47–1.62 (m, 2H,
CH2–CH2 CH3), 0.99 (t, 3H, J = 6.8 Hz, CH2 CH2–CH3)
8
6.62–7.26 (m, 12H) 4.12 (s, 2H) 2.81 [s, 2H, H2C C6H4 p-(NO2)], 7.47–8.2 [m, 4H, H2C
C6H4 p-(NO2), Ar–H].
9
6.66–7.77 (m, 12H) 4.27 (s, 2H) 1.86–2.89 (m, 2H , –H2C CH CH2), 5.98–6.16 (m, 1H,
H2C CH CH2), 5.25 (d, 2H, J = 12 Hz, H2C CH CH2)
10
6.08–7.05 (m, 12H) 4.21 (s, 2H) 1.12–1.27 (m, 2H, –H2C CH2 CH2 CH3), 1.31–1.38 (m, 2H,
H2C–CH2 CH2 CH3), 1.41–1.56 (m, 2H, H2C CH2–CH2 CH3),
0.88 (t, 3H, J = 6.8 Hz, H2C CH2 CH2–CH3)
11
12
6.07–7.27 (m, 12H) 4.30 (s, 2H) 1.38–1.46 (m, 2H, –CH2 CH3), 0.94 (t, 3H, J = 9.6 Hz, H2C–CH3)
6.64–7.17 (m, 12H) 4.27 (s, 2H) 1.68–1.88 [m, 1H, CH (CH3) CH2 CH3], 1.12 [d, H, J = 8.6 Hz, CH (CH3)
CH2 CH3], 1.26–1.42 [m, 2H, CH (CH3) CH2 CH3], 0.92 [t, 3H, J = 8.2
Hz, CH (CH3) CH2 CH3]
TABLE 3 13C NMR Data of 5–12
Compound
13C NMR Data
5
42.1 (C-4), 129.1 (C-5), 121. 1 (C-6), 128.9 (C-7), 115.6 (C-8), 129.0 (C-4a), 144.9 (C-8a), 144.9 (C-1ꢁ), 115.3
(C-2ꢁ), 134.4 (C-3ꢁ), 116.4 (C-4ꢁ), 129.7 (C-5ꢁ), 110.2 (C-6ꢁ), 147.1 (C-1ꢁꢁ), 116.8 (C-2ꢁꢁ and C-6ꢁꢁ),130.2 (C-3ꢁꢁ
and C-5ꢁꢁ), 127.0 (C-4ꢁꢁ), 20.2 (–H2C CH3), 16.9 ( H2C–CH3)
6
43.8 (C-4), 129.2 (C-5), 121.1 (C-6), 128.9 (C-7), 115.4 (C-8), 129.9 (C-4a), 147.2 (C-8a), 147.4 (C-1ꢁ), 115.5
(C-2ꢁ), 134.4 (C-3ꢁ), 116.9 (C-4ꢁ), 131.6 (C-5ꢁ), 111.7 (C-6ꢁ), 149.6 (C-1ꢁꢁ), 116.9 (C-2ꢁꢁ and C -6ꢁꢁ) , 130.8
(C-3ꢁꢁ and C-5ꢁꢁ), 127.2 (C-4ꢁꢁ), 30.8 [CH (CH3) CH2 CH3], 24.1 [CH (CH3) CH2 CH3], 34.6 [CH (CH3) CH2
CH3], 8.1 [CH (CH3) CH2 CH3]
7
8
44.2 (C-4), 129.2 (C-5), 121.2 (C-6), 129.0 (C-7), 115.6 (C-8), 129.2 (C-4a), 145.6 (C-8a), 147.2 (C-1ꢁ), 115.0
(C-2ꢁ), 134.7 (C-3ꢁ), 116.4 (C-4ꢁ), 130.2 (C-5ꢁ), 111.3 (C-6ꢁ), 148.9 (C-1ꢁꢁ), 116.8 (C-2ꢁꢁ and C-6ꢁꢁ), 129.5
(C-3ꢁꢁ and C-5ꢁꢁ), 127.3 (C-4ꢁꢁ), 46.0 (–H2C CH2 CH3), 27.3 ( H2C–CH2 CH3), 10.2 ( H2C CH2–CH3)
43.8 (C-4), 129.2 (C-5), 122.1 (C-6), 128.7 (C-7), 115.9 (C-8), 130.7 (C-4a), 147.2 (C-8a), 145.4 (C-1ꢁ), 113.5
(C-2ꢁ), 135.2 (C-3ꢁ), 117.8 (C-4ꢁ), 131.3 (C-5ꢁ), 116.5 (C-6ꢁ), 150.2 (C-1ꢁꢁ), 117.8 (C-2ꢁꢁ and C-6ꢁꢁ), 130.3
(C-3ꢁꢁ and C-5ꢁꢁ), 117.4 (C-4ꢁꢁ), 38.2 (CH2 Ar NO2), 145.2 (C-1ꢁꢁꢁ), 128.7 (C-2ꢁꢁꢁ and C-6ꢁꢁꢁ), 122.4 (C-3ꢁꢁꢁ and
C-5ꢁꢁꢁ), 147.2 (C-4ꢁꢁꢁ)
9
46.0 (C-4), 129.4 (C-5), 121.6 (C-6), 129.0 (C-7), 115. 6 (C-8), 129.9 (C-4a), 155.8 (C-8a), 134.9 (C-1ꢁ), 114.1
(C-2ꢁ), 134.7 (C-3ꢁ), 117.0 (C-4ꢁ), 130.7 (C-5ꢁ), 116.0 (C-6ꢁ), 31.4 (–H2C CH CH2), 130.3
( H2C–HC CH2), 116.8 ( H2C CH CH2), 155.7 (C-1ꢁꢁ), 117.3 (C-2ꢁꢁ and C-6 ꢁꢁ), 134.9 (C-3ꢁꢁ and C-5 ꢁꢁ),
117.0 (C-4 ꢁꢁ)
10
42.1 (C-4), 129.9 (C-5), 122.2 (C-6), 129.1 (C-7), 116.8 (C-8), 130.3 (C-4a), 155.0 (C-8a), 147.3 (C-1), 113.8
(C-2ꢁ), 134.8 (C-3ꢁ), 117.6 (C-4ꢁ) 130.4 (C-5ꢁ), 117.2 (C-6ꢁ), 150.0 (C-1ꢁꢁ), 119.7 (C-2ꢁꢁ and C-6ꢁꢁ), 129.9 (C-3ꢁꢁ
and C-5ꢁꢁ) 117.7 (C-4ꢁꢁ), 43.2 (–H2C CH2 CH2 CH3), 35.1 ( H2C–CH2 CH2 CH3), 20.5
( H2C CH2–CH2 CH3),13.2 ( H2C CH2 CH2–CH3)
11
12
42.3 (C-4), 129.9 (C-5), 129.4 (C-6), 121.2 (C-7), 115.8 (C-8), 130.2 (C-4a), 155.5 (C-8a), 148.5 (C-1ꢁ), 114.2
(C-2ꢁ), 134.6 (C-3ꢁ), 117.3 (C-4ꢁ), 131.9 (C-5ꢁ), 111.1 (C-6ꢁ), 150.6 (C-1ꢁꢁ), 117.3 (C-2ꢁꢁ and 6ꢁꢁ), 130.2 (C-3ꢁꢁ
and C-5ꢁꢁ), 127.1 (C-4ꢁꢁ), 27.3 (–CH2 CH3), 20.3 ( CH2–CH3)
46.2 (C-4), 129.3 (C-5), 129.0 (C-6), 120.8 (C-7), 115.9 (C-8), 130.3 (C-4a), 155.7 (C-8a), 153.7 (C-1ꢁ), 114.3
(C-2ꢁ), 135.0 (C-3ꢁ), 117.5 (C-4ꢁ), 132.0 (C-5ꢁ), 112.0 (C-6ꢁ), 154.5 (C-1ꢁꢁ), 117.5 (C-2ꢁꢁ and C-6ꢁꢁ), 130.3
(C-3ꢁꢁ and 5ꢁꢁ), 129.4 (C-4ꢁꢁ), 35.7 [CH (CH3) CH2 CH3], 23.1 [CH (CH3) CH2 CH3], 32.7 [CH (CH3) CH2
CH3], 8.5 [CH (CH3) CH2 CH3]
(hexane–ethyl acetate, 3:1). The solvent was removed
in a rota-evaporator. The crude iminophosphorane
(9) thus obtained was further purified by column
chromatography using silica gel (60–120 mesh) as
adsorbent and hexane and ethyl acetate (2:1) as an
eluent to afford analytically pure iminophosphorane
(9) as a solid. Other members of the series were pre-
pared by adopting the above procedure.
Heteroatom Chemistry DOI 10.1002/hc