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A. Marchenko et al. / Tetrahedron 66 (2010) 3668–3677
6.62 (2H, d, J¼8.0 Hz, Ar), 2.87 (s, 6H, NMe2), 2.67 (s, 3H, Me), 2.64
3.6.9. 1,1-Bis(dimethylamino)-N,N-dimethyl-N0-[3-(trifluoromethyl)-
(d, 12H, J¼9.5 Hz, NMe2); 13C NMR (125 MHz, CDCl3)
d
151.5 (d,
phenyl]phosphinecarboximidamide sulfide 18f. Yield 95%, oil; 1H NMR
J¼192.4 Hz), 147.8 (d, J¼21.4 Hz), 130.4, 128.9, 120.1, 40.5, and 36.4
(500 MHz, CDCl3)
d
7.30 (1H, dd, J¼7.5 Hz, 5H–Ar), 7.12 (1H, d,
(d, J¼4.0 Hz), 20.7; 31P NMR (81 MHz, CDCl3)
d
23.7. [Found: C,
J¼7.5 Hz, Ar), 6.97 (1H, br s, 2H–Ar), 6.91 (1H, d, J¼7.5 Hz, Ar), 2.91
56.90; N, 18.85; P, 10.57. C14H25N4OP requires C, 56.74; N, 18.91; P,
10.45].
(6H, s, NMe2), 2.72 (12H, d, J¼10.5 Hz, PNMe2); 13C NMR (125 MHz,
CDCl3)
d
153.2 (d, J¼154.7 Hz), 150.8 (d, J¼20.0 Hz), 130.8 (q,
J¼31.4 Hz), 128.8, 124.2 (q, J¼273.0 Hz), 123.5, 117.6 (q, J¼4.0 Hz),
3.6.3. 1,1-Bis(dimethylamino)-N,N-Dimethyl-N0-(4-methoxy-phe-
nyl)phosphinecarboximidamide oxide 17c. Yield 92%, mp 41–42 ꢁC
116.8 (q, J¼4.0 Hz), 41.6, 37.5; 31P NMR (81 MHz, CDCl3)
d
67.0; 19F
NMR (81 MHz, CDCl3)
d
ꢀ62.9. [Found: C, 46.04; N, 15.18; P, 8.26.
(pentane); 1H NMR (500 MHz, CDCl3)
d
6.76 (2H, d, J¼9.0 Hz, Ar),
C14H22F3N4PS requires C, 45.90; N, 15.29; P, 8.45].
6.65 (2H, d, J¼9.0 Hz, Ar), 3.75 (3H, s, MeO), 2.86 (6H, s, NMe2), 2.63
(12H, d, J¼9.6 Hz, NMe2); 13C NMR (125 MHz, CDCl3)
d
154.2, 151.7
3.6.10. 1,1-Bis(dimethylamino)-N,N-dimethyl-N0-[4-(trifluoro-
methyl)phenyl]phosphinecarboximidamide sulfide 18g. Yield 96%,
(d, J¼193.7 Hz), 143.5 (d, J¼22.6 Hz), 120.8, 113.4, 55.0, 40.1, 36.0;
31P NMR (81 MHz, CDCl3)
d
23.6. [Found: C, 53.62; N, 17.75; P, 10.20.
oil; 1H NMR (500 MHz, CDCl3)
d
7.33 (2H, d, J¼8.0 Hz, 3,5-H–Ar),
C14H25N4O2P requires C, 53.83; N, 17.94; P, 9.92].
6.71 (2H, d, J¼8.0 Hz, 2,6-H–Ar), 2.81 (s, 6H, NMe2), 2.61 (12H, d,
J¼10.5 Hz, PNMe2); 13C NMR (125 MHz, CDCl3)
d 153.5 (d,
3.6.4. 1,1-Bis(dimethylamino)-N,N-dimethyl-N0-[3-(trifluoro-
methyl)phenyl]phosphinecarboximidamide oxide 17f. Yield 86%; oil;
J¼19.0 Hz), 152.9 (d, J¼154.7 Hz), 125.4 (q, J¼4.0 Hz), 124.7 (q,
J¼27.0 Hz), 122.4 (q, J¼33.0 Hz), 120.0, 40.8 (d, J¼2.5 Hz), 37.3 (d,
1H NMR (500 MHz, CDCl3)
d
7.24 (1H, dd, J¼7.5 Hz, 5H–Ar), 7.05
J¼2.5 Hz); 31P NMR (81 MHz, CDCl3)
d
67.0; 19F NMR (188 MHz,
(1H, d, J¼7.0 Hz, Ar), 6.87 (1H, s, 2H–Ar), 6.81 (1H, d, J¼7.0 Hz, Ar),
CDCl3)
d
ꢀ62.2. [Found: C, 46.10; N, 15.16; P, 8.21. C14H22F3N4PS
2.88 (6H, s, NMe2), 2.54 (12H, d, J¼9.5 Hz, PNMe2); 13C NMR
requires C, 45.90; N, 15.29; P, 8.45].
(125 MHz, CDCl3)
d
152.5 (d, J¼183.6 Hz), 150.9 (d, J¼20.1 Hz),
128.8, 130.7 (q, J¼32.7 Hz), 124.2 (q, J¼273.0 Hz), 123.4, 117.5 (q,
3.6.11. 1,1-Bis(dimethylamino)-N,N-dimethyl-N0-1-naphthalenyl
J¼7.5 Hz), 116.7 (q, J¼7.5 Hz), 40.1 (d, J¼3.8 Hz), 36.2 (d, J¼5.0 Hz);
phosphinecarboximidamide sulfide 18i. Yield 81%, 117–118 ꢁC (pen-
31P NMR (81 MHz, CDCl3)
d
21.3. [Found: C, 47.88; N, 16.14; P, 9.13.
tane); 1H NMR (500 MHz, CDCl3)
d 8.01–8.03 (1H, m, Ar), 7.77–7.79
C14H22F3N4OP requires C, 48.00; N, 15.99; P, 8.84].
(1H, m, Ar), 7.43–7.45 (3H, m, Ar), 7.34 (1H, t, J¼7.5 Hz, Ar), 6.70 (1H,
d, J¼7.0 Hz, Ar), 2.87 (s, 6H, NMe2), 2.84 (12H, d, J¼3.0 Hz, PNMe2);
3.6.5. 1,1-Bis(dimethylamino)-N,N-dimethyl-N0-[4-(trifluoro-
methyl)phenyl]phosphinecarboximidamide oxide 17g. Yield 96%; oil;
13C NMR (125 MHz, CDCl3)
d
153.7 (d, J¼161.0 Hz), 147.3 (d,
J¼20.0 Hz), 134.2, 127.9, 127.3, 126.0, 125.8, 125.2, 124.6, 121.2, 113.5,
1H NMR (300 MHz, CDCl3)
d
7.46 (2H, d, J¼8.4 Hz, 3,5-H–Ar), 6.77
40.8 (d, J¼4.0 Hz), 37.8 (d, J¼2.5 Hz); 31P NMR (81 MHz, CDCl3)
(2H, d, J¼8.1 Hz, 2,6-H–Ar), 2.96 (6H, s, NMe2), 2.62 (12H, d,
d 68.3. [Found: C, 58.36; N, 15.95; P, 9.00. C17H25N4PS requires C,
J¼9.6 Hz, PNMe2); 13C NMR (125 MHz, CDCl3)
d
153.5 (d, J¼19.0 Hz),
58.60; N, 16.08; P, 8.89].
151.9 (d, J¼183.6 Hz), J¼270.4 Hz), 124.2 (q, 124.9, 122.0 (q,
J¼32.7 Hz), 119.6, 39.8, 35.5; 31P NMR (81 MHz, CDCl3)
d
22.2; 19F
3.6.12. 1,1-Bis(dimethylamino)-N,N-dimethyl-N0-phenylphos-
phinecarboximidamide selenide 19a. Yield 93%, 72–73 ꢁC (hexane);
NMR (81 MHz, C6D6)
C14H22F3N4OP requires C, 48.00; N, 15.99; P, 8.84].
d
ꢀ62.1. [Found: C, 47.86; N, 16.13; P, 9.08.
1H NMR (500 MHz, CDCl3)
d
7.22 (2H, dd, J¼7.5 Hz, Ph), 6.89 (1H, t,
J¼7.50 Hz, Ph), 6.76 (2H, d, J¼7.50 Hz, Ph), 2.87 (6H, s, Me2N), 2.77
3.6.6. 1,1-Bis(dimethylamino)-N,N-dimethyl-N0-1-naphthalenyl
phosphinecarboximidamide oxide 17i. Yield 94%; mp 93–94 ꢁC
(12H, d, J¼12.0 Hz, Me2NP); 13C NMR (125 MHz, CDCl3)
d 151.8 (d,
J¼148 Hz), 150.0 (d, J¼20.0 Hz), 128.4, 121.4, 120.3, 41.3 (d,
(hexane); 1H NMR (500 MHz, CDCl3)
d
7.93 (1H, d, J¼8.0 Hz, Ar),
J¼2.5 Hz), 38.0; 31P NMR (81 MHz, CDCl3)
d 70.2. [Found: C, 45.40;
7.71 (1H, d, J¼7.0 Hz, Ar), 7.37 (3H, m, Ar), 7.28 (1H, t, J¼7.5 Hz, Ar);
N, 16.45; P, 8.77. C13H23N4PSe requires C, 45.22; N, 16.23; P, 8.97].
6.59 (1H, d, J¼7.0 Hz, Ar), 2.82 (6H, s, NMe2), 2.61(12H, d, J¼9.5 Hz,
PNMe2); 13C NMR (125 MHz, CDCl3)
d
153.0 (d, J¼190.0 Hz), 147.3
3.6.13. 1,1-Bis(dimethylamino)-N,N-dimethyl-N0-(4-methylphe-nyl)-
phosphinecarboximidamide selenide 19b. Yield 92%; mp 85–86 ꢁC
(d, J¼20.1 Hz), 134.1, 127.8, 127.3, 125.8, 125.7, 125.0, 124.4, 121.1,
113.3, 40.3, 36.4; 31P NMR (81 MHz, CDCl3)
d
23.3. [Found: C, 61.60;
(pentane); 1H NMR (500 MHz, CDCl3)
d
7.33 (2H, d, J¼8.0 Hz, 2,6-
N, 16.74; P, 9.06. C17H25N4OP requires C, 61.43; N, 16.86; P, 9.32].
Ar), 6.68 (2H, d, J¼8.0 Hz, 3,5-Ar), 2.86 (6H, s, NMe2), 2.81 (12H, d,
J¼11.0 Hz, NMe2), 2.29 (3H, s, Me); 13C NMR (125 MHz, CDCl3)
3.6.7. 1,1-Bis(dimethylamino)-N,N-dimethyl-N0-phenylphosphine-
d
151.8 (d, J¼150.0 Hz), 147.4 (d, J¼20.0 Hz), 130.8, 129.0, 120.3, 41.3
carboximidamide sulfide 18a. Yield 93%, mp 44–45 ꢁC (pentane); 1H
(d, J¼3.8 Hz), 38.0, 20.8; 31P NMR (81 MHz, CDCl3)
d 66.9. [Found: C,
NMR (500 MHz, CDCl3)
d
7.22 (2H, dd, J¼7.5 Hz, 3,5-Ph), 6.89 (1H, t,
47.03; N, 15.65; P, 8.84. C14H25N4PSe requires C, 46.80; N, 15.59; P,
8.62].
J¼7.5 Hz, Ph), 6.76 (2H, d, J¼7.5 Hz, 2,6-Ph), 2.88 (6H, s, Me2N), 2.76
(12H, d, J¼12.0 Hz, Me2NP); 13C NMR (125 MHz, CDCl3)
d 152.3 (d,
J¼162.2 Hz), 150.3 (d, J¼20.1 Hz), 128.4, 121.3, 120.3, 41.1 (d,
3.6.14. 1,1-Bis(dimethylamino)-N0-(4-methoxyphenyl)-N,N-dimethyl-
J¼2.5 Hz), 36.4 (d, J¼3.8 Hz); 31P NMR (81 MHz, CDCl3)
d
69.0.
phosphinecarboximidamide selenide 19c. Yield 89%; bp 181–181/
[Found: C, 52.70; N, 18.63; P, 10.12. C13H23N4PS requires C, 52.33; N,
18.78; P, 10.38].
0.05 Torr, 69–70 ꢁC (pentane); 1H NMR (500 MHz, CDCl3)
d 6.82–
6.70 (4H, m, Ar), 3.73 (3H, s, MeO), 2.82 (6H, s, NMe2), 2.76 (12H, d,
J¼10.5 Hz, NMe2); 13C NMR (125 MHz, CDCl3)
d 154.7, 152.2 (d,
3.6.8. 1,1-Bis(dimethylamino)-N,N-dimethyl-N0-(4-methylphe-nyl)-
J¼151.0 Hz), 143.3 (d, J¼34.0 Hz), 121.4, 113.8, 55.5, 41.2, 38.1; 31P
phosphinecarboximidamide sulfide 18b. Yield 83%, mp 67–68 ꢁC
NMR (81 MHz, CDCl3) d 67.1. [Found: C, 44.53; N, 14.87; P, 8.32.
(pentane); 1H NMR (500 MHz, CDCl3)
d
7.02 (2H, d, J¼8.0 Hz, Ar),
6.67 (2H, d, J¼8.0 Hz, Ar), 2.85 (6H, s, Me2N), 2.76 (d,12H, J¼10.5 Hz,
Me2NP), 2.27 (3H, s, Me); 13C NMR (125 MHz, CDCl3)
152.3 (d,
C14H25N4OPSe requires C, 44.80; N, 14.93; P, 8.25].
d
3.6.15. 1,1-Bis(dimethylamino)-N0-(3-methoxyphenyl)-N,N-dimethyl-
J¼163.5 Hz), 147.7 (d, J¼22.6 Hz), 130.6, 129.0, 120.3, 41.1 (d,
phosphinecarboximidamide selenide 19d. Yield 84%, 160–165 ꢁC/
J¼4.0 Hz), 37.6 (d, J¼1.3 Hz), 20.8; 31P NMR (81 MHz, CDCl3)
d
69.3.
0.05 Torr; 1H NMR (500 MHz, CDCl3)
d
7.10 (1H, dd, J¼8.0 Hz, 5H–
[Found: C, 54.05; N, 17.90; P, 9.57. C14H25N4PS requires C, 53.82; N,
17.93; P, 9.91].
Ar), 6.45 (1H, m, Ar), 6.32–6.35 (2H, m, Ar), 3.77 (3H, s, MeO), 2.78
(12H, d, J¼11.0 Hz, NMe2); 13C NMR (125 MHz, CDCl3)
d 159.9, 151.8