NꢀCyanophenyl substituted aminomethylphosphines Russ.Chem.Bull., Int.Ed., Vol. 62, No. 11, November, 2013 2493
3
(s, H(7)); 6.91 (d, H(11), 3JH,H = 8.3 Hz) (total intensity 4 H);
(s, C(8)); 134.26 (s, C(10)); 149.86 (d, C(6), JP,C = 3.0 Hz).
31P NMR (DMF), : –29.51 (s).
3
6.99 (d, 2 H, H(9), JH,H = 7.6 Hz); 7.27 (dd, 2 H, H(10),
3
3JH,H = 8.3 Hz, JH,H = 7.6 Hz); 7.49—7.54 (m, 6 H, H(3),
(Mesityl)bis[Nꢀ(2ꢀcyanophenyl)aminomethyl]phosphine (6)
was obtained similarly to 5 from mesitylphosphine (1.82 g,
12.0 mmol), paraformaldehyde (0.72 g, 24.0 mmol), and 2ꢀaminoꢀ
benzonitrile (2.83 g, 24.0 mmol), the reaction time was 10 h.
The yield was 2.37 g (48%), m.p. 103—107 C. Found (%):
C, 72.48; H, 6.06; N, 13.47; P, 7.68. C25H25N4P. Calculated (%):
C, 72.82; H, 6.07; N, 13.59; P, 7.52. IR, /cm_–1 (KBr): 3376
(NH), 2209 (CN). 1H NMR (CDCl3), : 2.34 (s, 6 H, Me(5));
2.52 (s, 12 H, Me(3)); 4.50 (s, 4 H, H(1)); 6.36 (d, 2 H, H(11),
H(5)); 7.58—7.65 (m, 4 H, H(4)). 13C NMR (DMFꢀd7), : 58.10
1
(d, C(1), JP,C = 17.2 Hz); 113.05 (s, C(8)); 115.70 (s, C(7));
116.97 (s, C(11)); 119.55 (s, CN); 120.45 (s, C(9)); 129.33
3
3
(d, CA(4), JP,C = 3.7 Hz); 129.39 (d, CB(4), JP,C = 3.3 Hz);
2
129.85 (s, C(10)); 130.37 (s, C(5)); 132.70 (d, C(3), JP,C
=
= 20.32 Hz); 134.28 (d, C(2), 1JP,C = 13.6 Hz); 145.47 (s, C(6)).
31P NMR (DMF), : –50.62 (s).
1,5ꢀBis(4ꢀcyanophenyl)ꢀ3,7ꢀdimesitylꢀ1,5ꢀdiazaꢀ3,7ꢀdiphosꢀ
phacyclooctane (3) was obtained similarly to 1 from mesitylphosꢀ
phine (1.27 g, 8.4 mmol), paraformaldehyde (0.50 g, 16.7 mmol),
and 4ꢀaminobenzonitrile (0.99 g, 8.24 mmol), the reaction with
paraformaldehyde was carried out at 100—110 C, the reaction
time was 10 h. The yield of 3 was 1.65 g (67%), m.p. 215—220 C.
Found (%): C, 72.98; H, 6.50; N, 9.54; P, 10.19. C36H38N4P2.
Calculated (%): C, 73.47; H, 6.46; N, 9.52; P, 10.54. IR, /cm–1
(KBr): 2212 (CN). 1H NMR (CDCl3), : 2.34 (s, 6 H, Me(5));
2.51 (s, 12 H, Me(3)); 4.49 (s, 8 H, H(1)); 6.36 (d, 4 H, H(7),
3
3
3JH,H = 9.0 Hz); 6.86 (dd, 2 H, H(9), JH,H JH,H 9.0 Hz);
7.01 (br.s, 2 H, H(4)); 7.38 (d, 2 H, H(8), 3JH,H = 9.0 Hz) (the
signal for H(10) overlaps with the signal of CDCl3). 13C NMR
(CDCl3), : 20.99 (s, Me(5)); 23.61 (s, Me(3)); 23.73 (s, Me(3´));
56.69 (d, C(1), 1JP,C = 23.4 Hz); 98.97 (s, C(7)); 113.34 (s, C(11));
114.62 (s, C(9)); 120.17 (s, CN); 128.62 (d, C(3), 2JP,C = 23.9 Hz);
130.06 (s, C(10)); 133.15 (s, C(4), C(5)); 133.78 (s, C(2)); 140.78
(s, C(8)); 148.32 (s, C(6)). 31P NMR (DMF), : –37.39 (s).
3JH,H= 9.0 Hz); 7.00 (s, 4 H, H(4)); 7.39 (d, 4 H, H(8), 3JH,H
=
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 12ꢀ03ꢀ97083ꢀ
r_povolzh´e_a) and the Council on Grants at the Presiꢀ
dent of the Russian Federation (Program of State Support
for Leading Scientific Schools of the Russian Federation,
Grant NShꢀ6667.2012.3).
= 9.0 Hz). 13C NMR (CDCl3), : 21.05 (s, Me(5)); 23.67
1
(s, Me(3)); 56.76 (d, C(1), JP,C = 23.4 Hz); 99.01 (s, C(9));
113.37 (s, C(7)); 115.00 (s, C(3)); 120.22 (s, CN); 130.09
(s, C(8)); 133.21 (s, C(4)); 133.75 (s, C(5)); 140.84 (s, C(2));
148.33 (s, C(6)). 31P NMR (DMF), : –36.75 (s).
1,5ꢀBis(3ꢀcyanophenyl)ꢀ3,7ꢀdimesitylꢀ1,5ꢀdiazaꢀ3,7ꢀdiphosꢀ
phacyclooctane (4) was obtained similarly to 3 from mesitylphosꢀ
phine (1.75 g, 11.5 mmol), paraformaldehyde (0.69 g, 23.0
mmol), and 3ꢀaminobenzonitrile (1.36 g, 11.5 mmol). The yield
of 4 was 2.30 g (68%), m.p. 224—226 C. Found (%): C, 73.01;
H, 6.53; N, 9.10; P, 10.65. C36H38N4P2. Calculated (%): C, 73.47;
H, 6.46; N, 9.52; P, 10.54. IR, /cm–1 (KBr): 2224 (CN).
1H NMR (CDCl3), : 2.33 (s, 6 H, Me(5)); 2.53 (s, 12 H, Me(3));
References
1. G. Märkl, G. Yu. Jin, C. Schoerner, Tetrahedron Lett., 1980,
21, 1409.
2. B. A. Arbuzov, O. A. Erastov, G. N. Nikonov, Izv. Akad.
Nauk SSSR, Ser. Khim., 1980, 735 [Bull. Acad. Sci. USSR,
Div. Chem. Sci. (Engl. Transl.), 1980, 29].
3. A. A. Karasik, G. N. Nikonov, Zh. Obshch. Khim., 1993, 63,
2775 [J. Gen. Chem. (Engl. Transl.), 1993, 63].
4. A. A. Karasik, G. N. Nikonov, A. S. Dokuchaev, I. A. Litviꢀ
nov, Koordinats. Khim., 1994, 20, 300 [Russ. J. Coord. Chem.
(Engl. Transl.), 1994, 20].
5. A. A. Karasik, S. V. Bobrov, G. N. Nikonov, A. P. Pisarevskii,
I. A. Litvinov, A. S. Dokuchaev, Yu. T. Struchkov, K. M.
Enikeev, Koordinats. Khim., 1995, 21, 574 [Russ. J. Coord.
Chem. (Engl. Transl.), 1995, 21].
6. J. C. Kane, E. H. Wong, G. P. A. Jap, A. L. Rheingold,
Polyhedron, 1999, 18, 1183.
7. A. A. Karasik, R. N. Naumov, R. Sommer, O. G. Sinyashin,
E. HeyꢀHawkins, Polyhedron, 2002, 21, 2251.
8. A. A. Karasik, R. N. Naumov, O. G. Sinyashin, G. P. Belov,
H. V. Novikova, P. Lönnecke, E. HeyꢀHawkins, Dalton
Trans., 2003, 2209.
9. A. A. Karasik, Yu. S. Spiridonova, D. G. Yakhvarov, O. G.
Sinyashin, P. Lönnecke, R. Sommer, E. HeyꢀHawkins, Menꢀ
deleev Commun., 2005, 16, 89.
10. A. A. Karasik, R. N. Naumov, A. S. Balueva, Yu. S. Spiriꢀ
donova, O. N. Golodkov, H. V. Novikova, G. P. Belov, S. A.
Katsyuba, E. E. Vandyukova, P. Lönnecke, E. HeyꢀHawkꢀ
ins, O. G. Sinyashin, Heteroatom Chem., 2006, 17, 499.
11. A. D. Wilson, R. H. Newell, M. J. McNevin, J. T. Muckerꢀ
man, M. RakowskiꢀDuBois, D. L. DuBois, J. Am. Chem.
Soc., 2006, 128, 358.
2
2
4.44 (dd, 4 H, Heq(1), JH,H = 15.6 Hz, JP,H = 4.6 Hz); 4.52
(br.d, 4 H, Hax(1), 2JH,H = 15.6 Hz); 6.56 (m, 4 H, H(7), H(11));
6.95 (d, 2 H, H(9), 3JH,H = 7.6 Hz); 6.99 (s, 4 H, H(4)); 7.19 (dd,
2 H, H(10), 3JH,H = 7.6 Hz), 3JH,H = 9.2 Hz)). 31P NMR (DMF),
: –43.13 (s).
Bis[Nꢀ(2ꢀcyanophenyl)aminomethyl]phenylphosphine (5).
A mixture of phenylphosphine (1.67 g, 15.2 mmol) and paraformꢀ
aldehyde (0.91 g, 30.3 mmol) was heated to 90—100 C until it
became homogeneous. Then, bis(hydroxymethyl)phenylphosꢀ
phine was dissolved in deaerated benzene (20 mL) and 2ꢀaminoꢀ
benzonitrile (3.58 g, 30.3 mmol) was added. The reaction mixꢀ
ture was stirred at 100 C (a bath) for 8 h. A precipitate formed
was filtered off, washed with deaerated benzene, and dried over
3 h at 0.1 Torr. The yield was 3.03 g (54%), m.p. 156—158 C.
Found (%): C, 71.75; H, 4.79; N, 15.09; P, 8.13. C22H19N4P.
Calculated (%): C, 71.35; H, 5.14; N, 15.14; P, 8.38. IR, /cm–1
(KBr): 3378 (NH), 2212 (CN). 1H NMR (CDCl3), : 3.77 (dd,
2
2
2 H, HA(1), JH,H = 13.7 Hz, JP,H = 6.3 Hz); 3.83 (dd, 2 H,
2
2
HB(1), JH,H = 13.7 Hz, JP,H = 5.4 Hz); 4.70 (br.s, 2 H, NH);
6.69 (dd, 2 H, H(9), 3JH,H JH,H 7.7 Hz); 6.77 (d, 2 H, H(11),
3
3JH,H = 8.6 Hz); 7.37 (dd, H(10), 3JH,H = 7.7 Hz, 3JH,H = 8.6 Hz);
3
7.38 (d, H(8), JH,H = 7.7 Hz) (total intensity 4 H); 7.45—7.49
(m, 3 H, H(3), H(5)); 7.56—7.60 (m, 2 H, H(4)). 13C NMR
(CDCl3), : 40.39 (d, C(1), JP,C = 15.2 Hz); 96.59 (s, C(7));
1
111.36 (s, C(11)); 117.41 (s, C(9)); 117.52 (s, CN); 129.35
3
(d, C(4), JP,C = 7.1 Hz); 130.34 (s, C(5)); 132.55 (d, C(3),
1
2JP,C = 18.8 Hz); 132.60 (d, C(2), JP,C = 14.2 Hz); 132.84