4916
Y. Yamamoto et al. / Journal of Organometallic Chemistry 691 (2006) 4909–4917
NMR: d = 37.2. MS (EI) m/z (%): 375 (M+, 18), 360 (30),
B,B0,B00-Tri-n-hexyl-N,N0,N00-triethylborazine (EtN-B-
(n-C6H13))3 (6k): 1H NMR: d = 0.90–1.08 (m, 42H),
1.76–1.94 (m, 6H), 2.96 (q, J = 6.3 Hz, 6H). 13C NMR:
d = 24.9, 25.6, 25.7, 25.9, 31.5, 34.4, 34.8, 37.2. 11B
NMR: d = 36.5. MS (EI) m/z (%): 417 (M+, 70), 400
(100), 358 (33), 347 (74), 332 (48), 318 (57), 304 (31), 288
(44), 277 (50), 262 (24), 248 (54), 234 (41), 207 (24), 193
(33), 164 (61), 150 (20), 109 (22). HRMS: calc for
C24H54N311B3, [M]+ = 417.4597; found: 417.4601.
318 (75), 305 (100), 290 (37), 248 (20), 235 (17), 206 (17),
122
(28).
HRMS:
calc
for
C21H48N311B3,
[M]+ = 375.4127; found: 375.4122.
B,B0,B00-Tributyl-N,N0,N00-trimethylborazine (MeN-B-
(n-Bu))3 (6e): 1H NMR: d = 0.93 (t, J = 7.1 Hz, 9H),
1.02–1.06 (m, 6H), 1.29–1.45 (m, 12H), 2.94 (s, 9H). 13C
NMR: d = 14.0, 15.3, 26.4, 26.7, 33.6. 11B NMR:
d = 37.1. MS (EI) m/z (%): 291 (M+, 27), 249 (100), 207
(70), 165 (50), 122 (40), 81 (14). HRMS: calc for
C15H36N311B3, [M]+ = 291.3188; found: 291.3174.
3.7. Mixed alkylborazine (7)
Mixture of B,B0-di-i-butyl-N,N0,N00-trimethylborazine
(5f) and B,B0,B00-tri-i-butyl-N,N0,N00-trimethylborazine
A glass tube charged with B,B0-dicyclohexyl-N,N0,
N00-trimethylborazine (0.5 mmol), 1-hexene (3 mmol),
[RhCl(coe)2]2 (0.0075 mmol), t-Bu3P (0.033 mmol, P/
Rh = 2.1) in toluene (0.5 ml) was sealed under argon atmo-
sphere. The resulting mixture was stirred at 50 °C for 24 h.
The product was isolated by Kugelrohr distillation.
1
(MeN-B-(i-Bu))3 (6f): H NMR: d = 0.95 (d, J = 6.8 Hz),
0.96 (d, J = 6.3 Hz), 1.01 (d, J = 7.3 Hz), 1.07 (d,
J = 7.3 Hz), 1.80–1.96 (m, 5H), 2.96(s), 2.98 (s), 3.00 (s,
6H), 4.52 (bs). 13C NMR: d = 25.6, 25.65, 25.71, 25.9,
29.1, 34.5, 34.8, 37.2. 11B NMR: d = 34.5, 36.8. MS (EI)
m/z (%), 5f: 235 (M+, 64), 193 (100), 178 (52), 164 (30),
151 (51), 136 (37), 122 (37), 81 (19), 6f: 291 (M+, 97), 276
(35), 249 (100), 234 (47), 207 (56), 192 (24), 178 (26), 165
(21), 122 (32), 81 (18), HRMS: calc for C11H28N311B3
(5f), [M]+ = 235.2562; found: 235.2565, C15H36N311B3
(6f), [M]+ = 291.3188; found: 291.3182.
B,B0-(Dicylohexyl)-B00-n-hexyl-N,N0,N00-trimethylbor-
1
azine (7): H NMR: d = 0.90–0.96 (m, 3H), 1.01–1.05 (m,
2H), 1.31–1.38 (m, 14H), 1.50–1.77 (m, 16H), 2.99 (s,
6H), 3.03 (s, 3H). 13C NMR: d = 14.2, 22.7, 24.4, 27.3,
27.9, 28.6, 31.7, 33.3, 34.1, 34.7. 11B NMR: d = 36.9. MS
(EI) m/z (%): 371 (M+, 56), 316 (32), 301 (73), 246 (19),
233 (58), 206 (27), 165 (27), 150 (16), 122 (100), 81 (85).
HRMS: calc for C21H44N311B3, [M]+ = 371.3814; found:
371.3823.
Mixture of B,B0-bis(cyclohexylmethyl)-N,N0,N00-tri-
methylborazine (5g) and B,B0,B00-tris(cyclohexylmethyl)-
1
N,N0,N00-trimethylborazine (6g): H NMR: d = 0.92–1.30
(m), 1.52–1.85 (m), 2.99(s), 3.00 (s), 3.04 (s, 6H), 4.54
(bs). 13C NMR: d = 26.4, 26.5, 27.0, 27.1, 34.6, 34.9,
35.6, 35.8, 36.45, 36.48, 37.2. 11B NMR: d = 35.6. MS
(EI) m/z (%), 5g: 315 (M+, 31), 233 (100), 151 (43), 136
(17), 122 (24), 6g: 411 (M+, 36), 329 (100), 247 (58), 165
(37), 122 (24), HRMS: calc for C17H36N311B3,
References
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(b) L.G. Sneddon, in: W. Siebert (Ed.), Advances in Boron Chem-
istry, vol. 201, Royal Society of Chemistry, 1997, pp. 491–502;
(c) L. Maya, Appl. Organometal. Chem. 10 (1996) 175–182;
(d) K. Niedenzu, J.W. Dawson, Boron–Nitrogen Chemistry,
Springer-Verlag, Berlin, 1995;
(e) R.T. Paine, L.G. Sneddon, in: P. Wisian-Neilson, H.R.
Allcock, K.J. Wynne (Eds.), Inorganic and Organometallic
Polymers II, ACS Symposium Series 572, American Chemical
Society, Washington, DC, 1994, pp. 358–374;
(f) Y. Kimura, Y. Kubo, in: P. Wisian-Neilson, H.R. Allcock, K.J.
Wynne (Eds.), Inorganic and Organometallic Polymers II, ACS
Symposium Series 572, American Chemical Society, Washington,
DC, 1994, pp. 375–388;
[M]+ = 315.3188;
found:
315.3188,
C24H48N311B3,
[M]+ = 411.4127; found: 411.4117.
B-((4-tert-Butylcyclohexyl)methyl)-N,N0,N00-trimethyl-
borazine (4h): H NMR: d = 0.86 (s, 18H), 0.92–1.14 (m,
1
8H), 1.21–1.38 (m, 2H), 1.40–1.52 (m, 8H), 1.73 (m, 4H),
2.01 (m, 2H), 2.99 (s, 3H), 3.01 (s, 6H), 4.48 (s, broad,
1H). 13C NMR: d = 21.9, 27.5, 27.8, 29.3, 33.3, 37.2,
48.6. 11B NMR: d = 34.1. MS (EI) m/z (%): 207 (M+,
80), 178 (100), 150 (42), 122 (31). HRMS: calc for
C14H32N311B3, [M]+ = 275.2875; found: 275.2877.
(g) C.W. Allen, D.E. Brown, R.F. Hayes, R. Tooze, G.L. Poyser, in:
P. Wisian-Neilson, H.R. Allcock, K.J. Wynne (Eds.), Inorganic and
Organometallic Polymers II, ACS Symposium Series 572, American
Chemical Society, Washington, DC, 1994, pp. 389–397;
(h) R.T. Paine, L.G. Sneddon, CHEMTECH 24 (1994) 29–37;
(i) R.T. Paine, C.K. Narula, Chem. Rev. 90 (1990) 73–91;
(j) D.F. Gaines, J. Borlin, in: E.L. Muetterties (Ed.), Boron Hydride
Chemistry, Academic Press, New York, 1975, pp. 241–272;
(k) H. Steinberg, R.J. BrothertonOrganoboron Chemistry, vol. 2,
John Wiley & Sons, New York, 1966.
B,B0-Bis((4-tert-butylcyclohexyl)methyl)-N,N0,N00-tri-
methylborazine (5h): 1H NMR: d = 0.86 (s, 9H), 0.92–1.11
(m, 4H), 1.24–1.53 (m, 5H), 1.72 (m, 2H), 2.04 (m, 1H),
3.02 (s, 6H), 3.04 (s, 3H), 4.49 (d, broad, 2H). 13C NMR:
d = 21.9, 27.6, 27.8, 32.4, 32.6, 33.3, 36.9, 48.6. 11B
NMR: d = 37.1. MS (EI) m/z (%): 275 (M+, 22), 151
(21), 137 (100), 122 (55). HRMS: calc for C25H52N311B3,
[M]+ = 427.4440; found: 427.4438.
B,B0-Dicyclohexyl-N,N0,N00-trimethylborazine (5i): 1H
NMR: d = 1.21–1.40 (m, 6H), 1.47–1.78 (m, 16H), 3.04
(s, 9H). 13C NMR: d = 27.2, 27.8, 28.5, 34.8, 37.5. 11B
NMR: d = 36.1. MS (EI) m/z (%): 287 (M+, 75), 232
(57), 219 (100), 204 (31), 150 (25), 122 (81), 81(50). HRMS:
calc for C15H32N311B3, [M]+ = 287.2875; found: 287.2869.
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(2005) 14859–14866;
(b) T. Yamamoto, Y. Nakatani, T. Kamiyama, US Patent 0,177,002,
2005;
(c) T. Kumada, E. Nobutoki, K. Goto, M. Matsuura, JP Patent
186649, 2004.
[3] E. Framery, M. Vaultier, Heteroatom. Chem. 11 (2000) 218–225.