1
3
C, 49.7; H, 9.60; N, 17.4%). H NMR (C D , 500.13 MHz):
C(H)TMS}(tmen)] (1.17 g, 3.0 mmol) in diethyl ether (50 cm )
6
6
3
4
δ 6.22 (dd, J = 2.5 Hz, J = 2.3 Hz, 2H, N᎐CH), 5.01 [dt,
at Ϫ50 ЊC. The resulting yellow suspension was allowed to
warm to ambient temperature and stirred for 12 h. Evaporation
of volatiles in vacuo yielded a yellow powder (0.81 g). After 2 d
at ambient temperature colourless crystals of compound
6 (< 0.25 g, 42%), mp 65 ЊC (lit., 66 ЊC), separated from the
solid. H and C{ H} NMR and mass spectra were consistent
3
J = 3.9 Hz, 1H, NC(H)(CHR )N], 4.74 (br s, 1H, NH), 1.04 [d,
2
13
1
1
H, CH(TMS) ], 0.38 (s, 18H, 2 TMS). C{ H} NMR: δ 141
2
15
(
HCN), 71 [NC(H)(CHR )N], 25 [CH(TMS ) ], 2 (2 TMS). N
2 3 2
2 2
33
NMR (CDCl ): δ Ϫ130.2 (dd, J = 12.6 Hz, J = 3.4 Hz,
3
NH
NH
2
+
1
13
1
᎐
N), Ϫ252.4 (t, J = 9.9 Hz, NH). MS (EI): m/z 241 ([M] , 5),
26 ([M Ϫ Me] , 41), 199 ([M Ϫ Me Ϫ HCN] , 71), 168 ([M Ϫ
TMS] , 20), 146 (60), 127 (64), 82 {[M Ϫ (TMS) CH] , 90}, 73
[TMS] , 100). IR (Nujol): ν/cm 3132br (N–H), 1689s (C᎐N).
,2-Dihydro tautomer: H (C D CD , 500.13 MHz): δ 8.55
br s, 1H, NH), 7.49 (m, 1H), 6.49 (d, J = 4.5 Hz, 1H), 5.11 (dd,
᎐
NH
+
+
33
2
with the literature. An unidentified, air-sensitive by-product
+
+
1
gave the following NMR spectral data. H NMR (CDCl ):
2
3
+
Ϫ1
(
δ 4.27 (s, 1H, HCN), 3.24 (br s, 1H, NH), 0.13 (s, 9H, TMS),
Ϫ0.27 (s, 9H, TMS). C{ H} NMR (CDCl ): δ 96.8, 0.75,
Ϫ0.1. H NMR (C D ): δ 4.53 (s, 1H, HCNTMS), 3.20 (br s,
1
13
1
1
6
5
3
3
1
(
6
6
1
H), 1.11 (dd, J = 6.2 Hz, 1H), 0.33 (s, 18H).
1H, NH), 0.11 (s, 9H, TMS), Ϫ0.01 (s, 9H, TMS).
4
-Tris(trimethylsilyl)silyl-1,4-dihydro-1,3,5-triazine 3g. The
4-Phenyl-5-trimethylsilylpyrimidine 7.
A
solution of
compound [LiSi(TMS) (THF) ] (3.00 g, 7.5 mmol) was added
to a stirred suspension of 1 (0.61 g, 7.5 mmol) in diethyl ether
50 cm ) at Ϫ25 ЊC. Stirring was continued for 12 h; the reaction
mixture was quenched with H O (0.24 g, 13.3 mmol). The mix-
ture was quickly extracted with diethyl ether (2 × 10 cm ). The
combined organic layers were washed with water, dried
Na SO ) and concentrated in vacuo yielding 3g. Colourless,
feather-like crystals of 3g (1.63 g, 66%) were obtained from
[Li{N(TMS)C(Ph)C(TMS) }(THF) ] (2.00 g, 4.1 mmol) in
2
2
3
3
3
diethyl ether (ca. 10 cm ) was added to a stirred suspension of 1
(0.32 g, 4.0 mmol) at Ϫ80 ЊC. The reaction mixture was allowed
to warm to ambient temperature, stirred for 12 h and finally
refluxed for 2 h. The volatiles were removed in vacuo and the
residue was extracted with hot toluene. The precipitate
obtained from the toluene solution consisted of a mixture. This
3
(
2
3
(
2 4
Ϫ2
precipitate was sublimed at 65 ЊC (10 mbar) to afford a few
diethyl ether at Ϫ20 ЊC. Elemental analysis was consistent with
gؒOH2 (Found: C, 42.3; H, 9.61; N, 11.8. C H N OSi
4
colourless drops of an oil 7 (0.05 g), which, over the course of
1
3
3 d, crystallised. H NMR: δ 9.40 [s, 1H, NC(H)N], 8.81 [s, 1H,
12
33
3
1
requires C, 41.4; H, 9.56; N, 12.1%). H NMR (CDCl ): δ 6.07
NC(H)CTMS], 7.41–7.37 (m, 2H, o), 7.09 (m, 3H, m and p),
3
4
13
1
(
4
d, J = 2.6 Hz, 2H, N᎐CH), 5.57 [t, 1H, NC(H)(Si(TMS) )N],
Ϫ0.14 (s, 9H, TMS). C{ H} NMR: δ 172.6 (ipso, CTMS),
163.2 (NCH), 159.1 (NCH), 142.0 (ipso), 129.7 (ipso), 129.1,
3
13
1
.24 (br s, 1H, NH), 0.38 (s, 27H, Si(TMS) ). C{ H} NMR:
3
+
+
δ 140.4, 67.0, 1.7 (TMS). MS (EI): m/z 329 ([M] , 34), 287
128.3, 126.1 (p), Ϫ0.2 (TMS). MS (EI): m/z 228 ([M + H] ,
+
+
+
+
(
[M Ϫ CN H ] , 14), 256 ([M Ϫ TMS] , 12), 229 ([M Ϫ TMS Ϫ
HCN] , 48), 202 ([M Ϫ TMS Ϫ H C N ] , 25), 173 ([M Ϫ
TMS Ϫ C N H ] , 87), 73 ([TMS] , 100).
4.5%), 227 ([M] , 7.5), 213 ([M Ϫ Me] , 100), 197 (8), 160 (13),
2
2
+
+
+
73 ([TMS] , 26).
2
2
2
+
+
3
3
5
8
-tert-Butyl-1,9-bis(trimethylsilyl)-1,3,5,9-tetraazanona-
,4,6,8-tetraen-3-yllithium 8. 1,3,5-Triazine 1 (0.47 g, 5.8 mmol)
was added in one portion to a solution of [Li{N(TMS)-
1
4
-Bis(trimethylsilyl)methyl-1-trimethylsilyl-1,4-dihydro-1,3,5-
triazine 4. Bis(trimethylsilyl)methyllithium (0.70 g, 4.2 mmol)
was added in portions at 0 ЊC to a stirred solution of 1 (0.31 g,
.8 mmol) in diethyl ether (25 cm ). The white suspension was
allowed to warm to ambient temperature; stirring was con-
tinued for 5 h; the mixture was quenched with RCl (0.40 g,
.8 mmol). After stirring for 0.5 h, the volatiles were removed
in vacuo and vacuum distillation of the residue at 120 ЊC/10
mbar yielded the pale yellow waxy, crystalline solid 4 (0.90 g,
t
3
C(Bu )C(H)TMS}] (1.45 g, 2.9 mmol) in diethyl ether (40 cm )
2
3
at Ϫ50 ЊC. The yellow suspension was allowed to warm to
ambient temperature and stirred for 12 h. The suspension was
filtered and the filtrate concentrated in vacuo. Crystallisation of
the residue from hexane afforded the yellow powder 5 (0.85 g,
3
3
Ϫ2
4
4%), mp 139 ЊC (Found: C, 53.4; H, 9.12; N, 17.65. C H -
15 31
1
LiN Si requires C, 54.5; H, 9.45; N, 16.95%). H NMR (C D ,
4
2
6
6
3
33 K): δ 8.28 [s, 1H, NC(H)N], 8.17 [s, 1H, NC(H)N], 7.06 [d,
J = 13.1 Hz, 1H, C(H)=C(H)], 6.51 [d, 1H, C(H)=C(H)TMS],
7
6%) (Found: C, 48.7; H, 9.92; N, 13.8. C H N Si requires
13 31 3 3
1
3
C, 49.8; H, 9.96; N, 13.4%). H NMR (CDCl ): δ 7.04 (d,
3
4
3
1
.38 (s, 9H, CMe ), 0.35 (s, 9H, TMS), 0.21 (s, 9H, TMS).
J = 1.9 Hz, 2H, N᎐CH), 5.21 [dt, J = 3.3 Hz, 1H, NC(H)-
CH(TMS) }N], 0.65 [d, 1H, CH(TMS) ], 0.31 (s, 9H, NTMS),
.11 [s, 18H, CH(TMS)2]. C{ H} NMR (CDCl ): δ 142.1
2 N᎐CH), 70.5 [NC(H){CH(TMS) }N], 27.1 [CH(TMS) ], 1.3
TMS), Ϫ1.0 (TMS). MS (EI): m/z 313 ([M] , 9), 298
[M Ϫ Me] , 25), 240 ([M Ϫ TMS] , 40), 154 (88), 73 ([TMS] ,
00).
3
᎐
7
1
13
1
Li{ H} NMR (C D , 333 K): δ 0.71. C{ H} NMR (C D , 333
{
0
(
(
(
6
6
6
6
2
2
13
1
K): δ 181.3 [NC(H)N], 172.8 (ipso), 172.8 [NC(H)N], 147.7,
17.65, 42.5 (CMe ), 29.1 (CMe ), 2.1 (TMS), 0.6 (TMS). MS
3
1
(
(
3
3
᎐
2
2
+
t +
+
EI): m/z 337 ([M + Li] , 16), 273 ([M Ϫ Bu ] , 29), 188 (47), 168
+
+
+
71.5), 147 (92), 146 (89.5), 121 (100).
1
4
-tert-Butylpyrimidine 9. A solution of the lithium com-
pound 8 in benzene-d , in an NMR sample tube, was heated to
Treatment of dihydrotriazine 3f with H O or EtOH. The
6
2
1
4
6
0 ЊC for 90 h. H NMR: δ 9.26 [d, J = 0.7 Hz, 1H, NC(H)N],
3 t
dihydrotriazine 3f (1.91 g, 7.9 mmol) and [NH ]Br (2.39 g, 25.6
4
3
8.30 [d, J = 5.3 Hz, 1H, C(Bu )C(H)], 6.63 (dd, 1H, NCH),
1.16 (s, 9H, CMe ). C{ H} NMR: δ 177.5 (ipso), 158.7, 157.0,
3
mmol) were mixed in diethyl ether (30 cm ) with an excess of
13 1
3
water or ethanol (ca. 5 cm ) and stirred for 2 d at 40 ЊC. The
1
56.8, 116.6, 37.4 (CMe ), 29.2 (CMe ). Evaporation of the
organic layer was decanted off and carefully distilled yield-
3
3
solvent and redissolving the residue in CDCl yielded NMR
ing (TMS) O (74%) or EtOTMS (65%, GC), respectively; no
3
2
34
spectral data consistent with the literature.
attempt was made to separate the latter from ethanol.
Crystal data and refinement details for 3f†
2
-Phenyl-1,3,5-triazine 5. 1,3,5-Triazine 1 (0.14 g, 1.7 mmol)
was added in one portion to a solution of [Li{N(TMS)C(Ph)-
Crystal data for 3f: C H NSi , M = 241.49, orthorhombic,
10
23
2
3
NTMS}] (0.47 g, 0.9 mmol) in diethyl ether (15 cm ) at 0 ЊC.
2
space group P2 2 2 (No.19), a = 13.449(9), b = 13.597(3),
1 1 1
3 Ϫ1
The suspension was stirred for 12 h at ambient temperature.
c = 16.399(9) Å, V = 2999(3) Å , Z = 8, µ(Mo-Kα) = 2.2 cm ,
027 independent reflections were collected for 2 < θ < 28Њ on
an Enraf-Nonius CAD4 diffractometer with Mo-Kα radiation
The volatiles were removed in vacuo. The crude product
4
Ϫ2
was sublimed (ca. 45 ЊC/10 mbar) from the residue to give
9b
2
-phenyltriazine 5 (0.21 g, 81%), mp 65 ЊC (lit., 63–65 ЊC).
†
CCDC reference number 152354. See http://www.rsc.org/suppdata/
4
-Phenylpyrimidine 6. 1,3,5-Triazine 1 (0.27 g, 3.3 mmol) was
p1/b0/b008681i/ for crystallographic files in.cif or other electronic
format.
added in one portion to a solution of [Li{N(TMS)C(Ph)-
J. Chem. Soc., Perkin Trans. 1, 2001, 1103–1108
1107