3
Synthesis of R2PNCPh2 (R = Ph 1, i-Pr 2, Me 3)
CH(CH3)2), 1.38 (dd, 3H, CH(CH3)2, 3JPH = 10.2 Hz, JHH = 7.3
3
3
Hz), 1.34 (dd, 3H, CH(CH3)2, JPH = 10.2 Hz, JHH = 7.3 Hz),
0.98 (dd, 3H, CH(CH3)2, 3JPH = 14.7 Hz, 3JHH = 7.2 Hz), 0.79 (dd,
These compounds were prepared in a similar fashion and thus
only one preparation is detailed. A solution of benzophenone
imine (9.69 g, 53.5 mmol) and Et3N (6.77 mL, 48.6 mmol) in
diethyl ether (400 mL) was cooled to 0 ◦C before adding Ph2PCl
(8.72 mL, 48.6 mmol) dropwise. The reaction mixture turned
yellow and was stirred overnight. The suspension was filtered
and the solvent removed in vacuo. Purification via recrystallization
from acetonitrile afforded 1 as yellow crystals (12.4 g, 34.0 mmol,
3H, CH(CH3)2, JPH = 15.5 Hz, JHH = 7.1 Hz). 31P{ H} NMR
3
3
1
(CD2Cl2): 73.80. 13C{ H} NMR (CD2Cl2): 173.97, 173.91, 152.85,
1
152.82, 149.56, 149.38, 127.94, 127.52, 127.28, 126.57, 125.53,
82.78, 54.58, 54.47, 53.96, 53.69, 53.42, 53.15, 52.88, 50.92, 27.53,
26.99, 26.14, 25.49, 24.41, 24.03, 17.60, 17.58, 17.14, 17.11, 16.41,
16.38, 16.34, 16.31. C,H,N analysis calc. for C23H30NO2P (383.47):
C, 72.04; H, 7.89; N, 3.65. Found: C, 71.83; H, 8.05; N, 3.72. 6:
(642 mg, 1.96 mmol, 85%). Purification via recrystallization from
70%) 1H NMR (CD2Cl2) : 7.35–7.47 (m, 20H, Ph). 13C{ H} NMR
1
2
(CD2Cl2): 175.70 (d, (Ph)2CN, JCP = 13.7 Hz), 142.65 (2JCP
=
1
dichloromethane yields colourless needles. H NMR (CD2Cl2):
13.7 Hz, o-PPh2), 140.56 (d, o-PPh2,1JCP = 7.5 Hz), 132.48 (Ph),
7.48–7.54 (m, 4H, Ph), 7.22–7.26 (m, 2H, Ph), 7.12–7.18 (m, 3H,
Ph), 7.06–7.10 (tt, 1H, Ph), 4.17 (m, 1H, CHCO2CH3), 3.00 (s,
3H, CH3), 2.44 (m, 1H, CH2), 2.02–2.10 (m, 1H, CH2), 1.78
132.27 (Ph), 130.16 (Ph), 129.04 (Ph), 128.62–128.73 (m, Ph).
1
31P{ H} NMR (CD2Cl2) : 36.8. C,H,N analysis calc. for C25H20NP
(365.42): C, 82.17; H, 5.52; N, 3.83. Found: C, 82.02; H, 5.69; N,
2
2
(d, 3H, JPH = 14.0 Hz, P(CH3)2), 1.09 (d, 3H, JPH = 14.0 Hz,
1
3.88. 2: orange crystals (8.52 g, 28.7 mmol, 87.5%), H NMR
(CD2Cl2) : 7.38–7.47 (m, 10H, Ph), 1.89 (m, 2H, CH(CH3)2),
P(CH3)2). 31P{ H} NMR (CD2Cl2): 52.7. 13C{ H} NMR (CD2Cl2):
174.59, 151.56, 149.03, 148.78, 128.18, 128.08, 128.06, 127.50,
127.40, 126.32, 126.28, 82.97, 66.22, 51.45, 31.00, 30.57, 19.20,
18.62, 17.02, 16.28, 15.67. C,H,N analysis calc. for C19H22NO2P
(327.36): C, 69.71; H, 6.77; N, 4.28. Found: C, 71.09; H, 7.05;
N, 4.52.
1
1
3
3
1.09 (dd, 6H, CH(CH3)2, JHH = 7.4 Hz, JPH = 14.8 Hz), 1.00
(dd, 6H, CH(CH3)3, JHH = 7.4 Hz, JPH = 14.8 Hz). 13C{ H}
NMR (CD2Cl2) : 177.27 (d, (Ph)2CN, 2JCP = 13.7 Hz), 141.04 (d,
Ph,1JCP = 7.5 Hz), 129.90 (s, Ph), 129.16 (s, Ph), 129.14 (s, Ph),
128.49 (s, Ph), 27.55 (m, CH(CH3)2), 19.09 (s, CH(CH3)2), 18.90
3
3
1
(s, CH(CH3)2), 18.61 (s, CH(CH3)2), 18.51 (s, CH(CH3)2). 1P{ H}
1
Synthesis of R2PNCPh2(CCO2Me)2 (R = Ph 7, i-Pr 8)
NMR (CD2Cl2): 68.6. C,H,N analysis calc. for C19H24NP (297.38):
C, 76.74; H, 8.13; N, 4.91. Found: C, 76.75; H, 8.10; N, 5.04. X-Ray
quality crystals were grown from cooling a saturated diethyl ether
solution to -35 ◦C. 3: orange oil 1H NMR (C6D6): 7.49–7.51 (m,
4H, Ph), 7.06–7.09 (m, 6H, Ph), 1.07 (d, 6H, CH3, 2JPH = 4.7 Hz)
These compounds were prepared in a similar fashion and thus only
one preparation is detailed. Compound 1 (365 mg, 1.0 mmol) was
dissolved in diethyl ether (5 mL) to which dimethyl acetylenedi-
carboxylate (150 mg, 1.05 mmol) dissolved in diethyl ether (5 mL)
was added dropwise. The reaction turned from light yellow to
light orange with a precipitate forming in 10 min. The reaction
was stirred overnight. The reaction was filtered and washed with
cold pentane (15 mL) to give a pure yellow powder 7 (380 mg,
.75 mmol, 75%). 1H NMR (CD2Cl2): 7.56–7.61 (m, 6H, Ph), 7.42–
7.46 (m, 4H, Ph), 7.29–7.32 (m, 4H, Ph), 7.22–7.25 (m, 6H, Ph),
1P{ H} NMR (C6D6): 27.81 (31P{ H} NMR shows 93% purity).
Attempts to purify were unsuccessful, thus the crude product was
used as prepared in subsequent reactions.
1
1
Synthesis of R2PNCPh2(CH2CH(CO2Me)) (R = Ph 4, i-Pr 5,
Me 6)
3.68 (s, 3H, CH3), 3.59 (s, 3H, CH3). 31P{ H} NMR (CD2Cl2):
1
1
These compounds were prepared in a similar fashion and thus only
one preparation is detailed. 1 (731 mg, 2.0 mmol) was completely
dissolved in diethyl ether (5 mL) before the addition of methyl
acrylate (181 mg, 2.10 mmol). The yellow colour of the solution
faded to a clear solution and a white precipitate formed. The
solution was stirred overnight. The solution was filtered and
washed with cold pentane (15 mL) to afford 4 as a white solid
(772 mg, 1.71 mmol, 85.5%). 1H NMR (CD2Cl2) : 7.02–7.38, 7.46–
7.61, 7.88–7.97 (m, 20H, Ph), 4.25–4.37 (m, 1H, CHCO2CH3),
2.93–3.03 (m, 4H, CH3 and CH2 trans to CO2Me), 2.70–2.85 (m,
49.04. 13C{ H} NMR (CD2Cl2): 176.71, 176.33, 166.57, 166.33,
162.48, 162.36, 146.58, 146.51, 132.60, 132.50, 132.18, 132.16,
128.40, 128.30, 128.16, 127.36, 126.62, 88.08, 52.49, 52.28, 43.92.
C,H,N analysis calc. for C31H26NO4P (507.52): C, 73.36; H, 5.16;
N, 2.76. Found: C, 72.91; H, 5.59; N, 2.71. 8: orange powder
(1.20 g, 2.73 mmol, 75%). Orange crystals (8.52 g, 28.7 mmol,
1
88%), H NMR (CD2Cl2): 7.84–7.87 (m, 2H, Ph), 7.65–7.68 (m,
2H, Ph), 7.27–7.49 (m, 6H, Ph), 4.32 (m, 1H, CHCOOCH3),
3.30 (s, 3H, CH3), 2.66–2.77 (m, 2H, CH(CH3)2), 2.37 (m, 1H,
CH2), 1.83–1.93 (m, 1H, CH2), 1.55–1.63 (m, 6H, CH(CH3)2),
1H, CH2 cis to CO2CH3). 13C{ H} NMR (CD2Cl2) : 173.5 (d,
1.20 (dd, 3H, CH(CH3)2,3JPH = 15.9 Hz, JHH = 7.3 Hz), 1.01
1
3
3
1
J = 6 Hz), 150.95, 148.63, 148.43, 132.26, 132.17, 131.57, 131.55,
131.11, 131.01, 130.74, 130.71, 128.22, 128.10, 128.02, 127.97,
127.91, 127.42, 127.14, 126.80, 125.92, 125.58, 82,89, 50.90, 31.85,
(dd, 3H, CH(CH3)2,3JPH = 16.9 Hz, JHH = 7.2 Hz). 13C{ H}
NMR (CD2Cl2) : 173.95, 152.85, 149.48, 127.94, 127.52, 127.28,
126.57, 125.53, 82.77, 54.54, 50.92, 27.27, 25.79, 24.22, 17.61,
31.40. 31P{ H} NMR (CD2Cl2): 48.61. C,H,N analysis calc. for
17.34, 16.37. 1P{ H} NMR (CD2Cl2): 73.79 C,H,N analysis calc.
1
1
C29H26NO2P (451.51): C, 77.15; H, 5.80; N, 3.10. Found: C, 76.62;
H, 5.89; N, 3.19. X-Ray quality crystals were grown by slow
diffusion of pentane into a saturated dichloromethane solution.
for C25H30NO4P (439.48): C, 68.32; H, 6.88; N, 3.19. Found: C,
68.43; H, 6.66; N, 3.65. X-Ray quality crystals were grown by slow
cooling of a saturated diethyl ether solution.
1
5: (800 mg, 2.02 mmol, 63%) white solid, H NMR (CD2Cl2):
7.62–7.63 (m, 2H, Ph), 7.42–7.45 (m, 2H, Ph), 7.25 (tt, 2H, J =
8 Hz, Ph), 7.12–7.16 (m, 3H, Ph), 7.06 (tt, 1H, J = 7 Hz, Ph),
4.05–4.13 (m, 1H, CHCO2CH3), 3.08 (s, 3H, CH3), 2.45–2.54
(m, 2H, CH2), 2.08–2.18 (m, 1H, CH(CH3)2), 1.63–1.68 (m, 1H,
Synthesis of R2PNCPh2(CH2CH(CN)) 9
Compound 1 (1.096 g, 3.00 mmol) was dissolved in diethyl ether
(10 mL) to which acrylonitrile (160 mg, 3.03 mmol) dissolved
This journal is
The Royal Society of Chemistry 2010
Dalton Trans., 2010, 39, 9626–9632 | 9627
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