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Y. A. Aze6 et al. / Tetrahedron Letters 44 (2003) 8689–8691
Scheme 2.
Synthesis of the carboranes was achieved by heating the
propargyl derivatives 4, 6, 10, and 11 with decaborane
and acetonitrile in toluene for 15–18 h in analogy to the
procedure described elsewhere.6 After evaporation of
the reaction solution the corresponding boron-contain-
ing derivatives 7, 8, 12, and 13 were obtained (Schemes
1 and 2).
boiling ethanol the corresponding monoaminoderiva-
tives of 4,6-dipropargyloxy-s-triazine 4a,b were
obtained.†
The synthesis of diaminopropargylderivatives was car-
ried out conveniently in another way. Thus, interaction
of cyanuric chloride 1 with morpholine at a stepwise
increase of temperature from 0 to 40°C gives the known
2,4-dimorpholyl-6-chloro-s-triazine 5.5 2,4-Dimor-
pholyl-6-propargyloxy-s-triazine 6 was obtained by
reaction of 5 with propargyl alcohol with alkali at
40–45°C.
o-Carboranyl derivatives of 1,3,5-s-triazines have been
described recently.7 The derivatives described here were
obtained by the addition of decaborane to a triple
bond, and contain an additional methylene group
between the triazine ring and the carborane, whereas
the structures described in Ref. 7 have been obtained by
the action of lithium carboranes with cyanuric
chlorides.
We synthesized the 2,4,6-tripropargylthioderivative 10
by interaction of the thiocyanuric acid 9 in 2% aqueous
NaOH with propargyl bromide at room temperature
for 3 h (Scheme 2). Upon heating of 10 with morpho-
line in boiling ethanol, the corresponding morpholyl
derivative 11 was produced.
The electron impact (EI) mass spectra of the propargyl-
oxy and propargylthio derivatives of 1,3,5-triazine
show fragment ions [M−OCH2−CCH]+ and [M−CH2−
CCH]+, resulting from cleavages of the bonds on both
sides of the O- or S-atom.
† All new compounds gave satisfactory mass spectra. Spectra with
boron fragments gave the expected isotope distribution pattern.
These ions are indicated with ‡. Structure was established by 1H
NMR. Indicated are: no. of compound, yield %, mp °C (solvent for
crystallization). molecular ion mass, m/z (relative intensity, %). 1H
NMR in DMSO-d6, 200 MHz: 4a, 45–50. 108–109 (ethanol). 274
For the aminopropargyl cyanurates 4a,b we observed
an unusual fragmentation of the molecular ion. Both
molecules gave intensive fragment ions at [M−92]+
(26), [M]+ . 3.55 (t, 2H, J=2.4 Hz, 2×CH), 3.60–3.75 (m, 8H,
4×CH2), 4.96 (d, 4H, J=2.4 Hz, 2×OCH2). 4b, 45–50, 104–105
(ethanol). 272 (21), [M]+ . 1.40–1.70 (m, 6H, 3×CH2), 3.55 (br. s,
2H, 2×CH), 3.60–3.80 (br. s, 4H, 2×CH2), 4.93 (br. s, 4H, 2×
OCH2). 6, 30–35, 124–125 (ethanol). 305 (30), [M]+ . 3.50 (br. s, 1H,
CH), 3.55–3.80 (m, 16H, 8×CH2), 4.90 (br. s, 2H, OCH2). 7a,
40–45, 115–116 (acetic acid). 511‡ (100), [M]+ . −0.5–+4.0 (br. m,
20H, 2×B10H10), 3.55–3.85 (m, 8H, 4×CH2), 4.92 (br. s, 4H, 2×
OCH2), 5.24 (br. s, 2H, 2×CH). 7b, 40–45, 160–161 (acetic acid).
509‡ (100), [M]+ . −1.5–+4.5 (br. m, 20H, 20×B10H10); 1.30–1.70 (m,
6H, 3×CH2), 3.74 (br. s, 4H, 2×CH2), 4.93 (br. s, 4H, 2×OCH2),
5.26 (br. s, 2H, 2×CH). 8, 20–25, 145–146 (precipitation from acetic
acid by water). 424‡ (100), [M]+ . 0–+4.5 (br. m, 10H, B10H10),
3.20–4.00 (m, 16H, 8×CH2), 4.88 (br. s, 2H, OCH2), 5.24 (br. s, 1H,
CH). 10, 70–75, 77–78 (ethanol). 291 (3), [M]+ . 3.22 (t, 3H, J=2.4
Hz, 3×CH), 4.02 (d, 6H, J=2.4 Hz, 3×SCH2). 11, 70–75, 114–115
(ethanol). 306 (1), [M]+ . 3.16 (, 2H, J=2.4 Hz, 2×CH), 3.45–3.80
(m, 8H, 4×CH2), 3.92 (d, 4H, J=2.4 Hz, 2×SCH2). 12, 25–30,
150–151 (precipitation from acetic acid by water). 646‡ (23), [M]+
.
0–+4.5 (br. s, 30 H, 3×B10H10), 4.19 (br. s, 6H, 3×SCH2), 5.18 (br.
s, 3H, 3× CH). 13, 35–40, 128–130 (precipitation from acetic acid by
water). 542‡ (66), [M]+ . 0.4–4.5 (br. s, 20H, 2×B10H10), 3.50–4.00
(m, 8H, 4×CH2), 4.13 (br. s, 4H, 2×CH2), 5.16 (br. s, 2H, 2×CH).
Scheme 3.