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Nifant´ev et al.
pꢀН, Ph); 3.89 (d, 3 Н, Me, 4JP,H = 12.1 Hz); 3.32 (d, 3 Н, Me,
4JP,H = 5.9 Hz). 13С NMR (100 MHz, CDCl3), δ: 190.99 (d,
I(1)
1
2
P—C=N, JС,Р = 39.7 Hz); 134.88 (d, oꢀPh, JС,Р = 21.6 Hz);
3
131.09 (s, pꢀPh); 129.53 (d, mꢀPh, JС,Р = 9.0 Hz); 127.44 (d,
1
3
P—Cipso, JС,Р = 1.8 Hz); 54.41 (d, Me, JС,Р = 2.9 Hz); 46.62
(d, Me, 3JС,Р = 10.5 Hz). Found (%): С, 48.29; Н, 5.08; N, 3.75;
P, 8.53; I, 34.75. C15H17NPI. Calculated (%): С, 48.80; Н, 4.62;
N, 3.80; P, 8.39; I, 34.38.
C(6)
C(5)
C(7)
C(14)
N(1)
P(1)
Compounds 3b and 3с were synthesized similarly. In both
cases, the reaction time was 48 h.
C(1)
N,NꢀDiethyl(diphenylphosphinomethylene)iminium iodide
(3b), the yield was 45%, yellow needles, m.p. 78—80 °C.
31Р NMR (162 MHz, CDCl3), δ: –5.80. 1Н NMR (400 MHz,
CDCl3), δ: 9.90 (m, 1 Н, N=СН); 7.82 (m, 4 Н, oꢀН); 7.49 (m,
C(2)
C(4)
C(15)
C(3)
C(8)
6 H, m,pꢀН); 4.27 (m, 2 H, СН2); 3.71 (q, 2 Н, СН2, JH,H
=
6.8 Hz); 1.48 (d, 3 H, Me, 3JH,H = 7.2 Hz, JP,H = 1.6 Hz); 1.06
C(9)
C(10)
3
(d, 3 H, Me, JH,H = 7.2 Hz, JP,H = 2.3 Hz). 13С NMR
C(13)
C(12)
(100 MHz, CDCl3), δ: 188.87 (d, P—C=N, JС,Р = 40.5 Hz);
134.54 (d, oꢀPh, JС,Р = 21.5 Hz); 132.67 (s, pꢀPh); 129.3 (d,
mꢀPh, JС,Р = 11.7 Hz); 128.27 (d, P—Cipso, JС,Р = 2.2 Hz);
56.90 (d, СН2, JС,Р = 2.2 Hz); 52.20 (d, СН2, JС,Р = 10.5 Hz);
13.55 (d, Me, JС,Р = 1.8 Hz); 10.10 (s, Me). Found (%): С, 51.43;
Н, 5.26; N, 3.55; P, 7.71; I, 31.99. C17H21NPI. Calculated (%):
С, 51.40; Н, 5.33; N, 3.53; P, 7.80; I, 31.93.
N,Nꢀdiisopropyl(diphenylphosphinomethylene)iminium iodide
(3с), the yield was 24%, lemon yellow needles, m.p. 152—154 °C.
31Р NMR (162 MHz, CDCl3), δ: –8.60. 1Н NMR (400 MHz,
CDCl3), δ: 9.55 (m, 1 Н, N=СН); 7.68 (m, 4 Н, oꢀН); 7.48 (m,
C(11)
Fig. 1. General view of compound 3а with atoms represented by
thermal ellipsoids of vibrations (p = 50%).
Table 1. The main bond lengths (d) and bond angles (ω) in
compound 3a
6 H, m,pꢀН); 4.61 (sept.d, 1 Н, N—СН, JH,H = 6.6 Hz, JP,H
=
1.4 Hz); 4.56 (sept.d, 1 Н, N—СН, JH,H = 6.7 Hz, JP,H
=
1.8 Hz); 1.62 (dd, 6 H, Me, JH,H = 6.6 Hz, JP,H = 1.7 Hz); 1.21
(d, 6 H, Me, JH,H = 6.6 Hz). 13С NMR (100 MHz, CDCl3), δ:
Bond
d/Å
Angle
ω/deg
P(1)—C(1)
P(1)—C(8)
P(1)—C(2)
1.807(6)
1.826(6)
1.838(6)
C(1)—P(1)—C(8)
C(1)—P(1)—C(2)
C(8)—P(1)—C(2)
106.3(3)
98.8(2)
103.5(3)
188.35 (d, P—C=N, JС,Р = 42.6 Hz); 133.8 (d, oꢀPh, JС,Р
20.8 Hz); 130.57 (s, pꢀPh); 129.11 (d, mꢀPh, JС,Р = 8.4 Hz);
127.45 (d, P—Cipso, JС,Р = 13.1 Hz); 62.18 (d, N—СН, JС,Р
=
=
N(1)—C(1) 1.289(7)
N(1)—C(15) 1.455(7)
N(1)—C(14) 1.475(7)
I(1)…—C(1) 3.526(2)
C(1)—N(1)—C(15) 123.2(5)
C(1)—N(1)—C(14) 121.4(5)
C(15)—N(1)—C(14) 115.4(5)
16.0 Hz); 56.37 (s, N—СН); 23.40 (s, Me); 17.64 (s, Me).
Found (%): С, 53.51; Н, 5.86; N, 3.30; P, 7.33; I, 29.96.
C19H25NPI. Calculated (%): С, 53.66; Н, 5.93; N, 3.29; P, 7.28;
I, 29.84.
N(1)—C(1)—P(1)
127.8(5)
References
nium chloride1 and N,Nꢀdiisopropyl[bis(diisopropylꢀ
amino)phosphinomethylene]iminium dichlorophosꢀ
phate,3 synthesized earlier by other methods.
1. O. I. Kolodyazhnyi and A. I. Chernega, Zh. Obshch. Khim.,
1992, 62, 2670 [Russ. J. Gen. Chem., 1992, 62 (Engl. Transl)].
2. M. Joleibhavoup, A. Baceiredo, O. Traitler, R. Ahlrichs,
M. Nieger, and G. Bertrand, J. Am. Chem. Soc., 1992, 114,
10559.
3. J. Youmri, Y. Leridu, H. Gornitzka, A. Baceidero, and
G. Bertrand, Eur. J. Inorg. Chem., 1998, 10, 1539.
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5. S. Conejero, Y. Canac, F. S. Than, and G. Bertrand, Ang.
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6. Sh. A. Samsoniya, Khim. Geterotsikl. Soedin, 1982, 2, 206
[Chem. Heterocycl. Compd., 1982, 2 (Engl. Transl.)].
N,NꢀDimethyl(diphenylphosphinomethylene)iminium iodide
(3a). Chlorodiphenylphosphine (2) (4.1 mL, 5 g, 0.023 mol) and
NaI (3.5 g, 0.023 mol) were added to DMF (1a) (7 mL, 6.58 g,
0.09 mol) with stirring and in the atmosphere of an inert gas.
The reaction mixture was stirred for 10 h at 20 °C and diluted
with CH2Cl2 (30 mL). The precipitate that formed after 2 h was
filtered off and washed with CH2Cl2 (2×5 mL). The combined
filtrate was concentrated in vacuo, benzene (30 mL) was added
to the oily residue, the precipitate that formed was reprecipitated
from DMF with benzene, and then from CH2Cl2 with benzene,
filtered, washed with benzene (2×5 mL), and dried in vacuo.
Compound 3а (3.35 g, 41%) was obtained as light yellow needleꢀ
like crystals, m.p. 140—141 °C (decomp.). 31Р NMR (162 MHz,
CDCl3), δ: –3.42. 1Н NMR (400 MHz, CDCl3), δ: 9.88 (m,
1 Н, N=СН); 7.79 (m, 4 Н, С6Н5, oꢀН); 7.45 (m, 6 H, mꢀН,
Received July 19, 2007;
in revised form August 23, 2007