and Et2NH (each 1.0 mol dmϪ3) in CHCl3 (containing 0.05 mol
dmϪ3 Me2NH2ϩ ClϪ and Et2NH2ϩ ClϪ) (250 µl) at 30 ЊC (sealed
ampoule for 5a). The NMe2 : NEt2 product ratio was deter-
mined by 31P NMR spectroscopy after 3 h (for 5b) or 9 days (for
5a; some substrate still present).
References
1 F. I. Luknitskii and B. A. Vovsi, Russ. Chem. Rev., 1969, 38, 487;
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Phosphonothioic diamide products
The identities of the products formed in the rate studies were
confirmed as detailed below.
3 Chemistry of Organophosphorus Compounds, ed. F. R. Hartley,
Wiley, Chichester, 1996, vol. 4.
From 5a and Me2NH, product 6a (R = Me), crystallised from
light petroleum, mp 104.5–105.5 ЊC; m/z 318 (Mϩ, 1.5%) and
151 (Mϩ Ϫ Ph2CH, 100); δP (CDCl3) 85.7; δH (CDCl3, 250
MHz) 7.8–7.7 (4 H, m), 7.35–7.15 (6 H, m), 4.64 (1 H, d, JPH 18)
and 2.43 (12 H, d, JPH 11) (Found: C, 64.4; H, 7.3; N, 8.7; Mϩ,
318.1319. C17H23N2PS requires C, 64.1; H, 7.3; N, 8.8%; M,
318.1320).
From 5a and Et2NH, product 6a (R = Et), purified by
chromatography (silica; 1 : 1 CH2Cl2–light petroleum) and
crystallisation from ether–light petroleum, mp 101.5–103.5 ЊC;
m/z 346 (Mϩ, 1.5%) and 179 (Mϩ Ϫ Ph2CH, 100); δP (CDCl3)
83.1; δH (CDCl3; 250 MHz) 7.8–7.7 (4 H, m), 7.3–7.15 (6 H, m),
4.68 (1 H, d, JPH 18), 3.01 (4 H, dq, JPH 11, JHH 7), 2.46 (6 H, d,
JPH 11) and 0.86 (6 H, t, JHH 7) (Found: Mϩ, 346.1632;
C19H27N2PS requires M, 346.1633).
From 5b and Me2NH, product 6b (R = Me), non-crystalline
(glass), m/z 363 (Mϩ, 0.3%) and 151 (Mϩ Ϫ ArPhCH, 100);
δP (CDCl3) 84.3; δH (CDCl3, 250 MHz) 8.15 (2 H, d, JHH 8.5),
7.95 (2 H, d, JPH 1.5, JHH 8.5), 7.75–7.65 (2 H, m), 7.35–7.2
(3 H, m), 4.76 (1 H, d, JPH 18), 2.45 (6 H, d, JPH 11.5) and
2.44 (6 H, d, JPH 11.5); νmax (film)/cmϪ1 1520 and 1350
(NO2) (Found: Mϩ, 363.1170; C17H22N3O2PS requires M,
363.1170).
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From 5b and Et2NH, product 6b (R = Et) (mixture of
diastereoisomers), non-crystalline, m/z 391 (Mϩ, 0.5%) and 179
(Mϩ Ϫ ArPhCH, 100); δP (CDCl3) 81.5 (major) and 81.3;
δH (CDCl3, 250 MHz) 8.13 (2 H, d, JHH 9), 8.0–7.9 (2 H, m),
7.8–7.7 (2 H, m), 7.35–7.2 (3 H, m), 4.815 (major) and 4.805
(total 1 H; both d, JPH 18), 3.1–2.9 (4 H, m), 2.495 (major) and
2.475 (total 6 H; both d, JPH 11), and 0.91 and 0.86 (major)
(total 6 H; both t, JHH 7); νmax (film)/cmϪ1 1520 and 1350 (NO2)
(Found: Mϩ, 391.1483. C19H26N3O2PS requires M, 391.1483).
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493