1
554
J. Taubitz and U. Lüning
+
[
(
(
M − C2H5] , 136 (100). m/z (CI, isobutane) 326 (16%), 284
(t, –OCH2–), 70.3 (t, –OCH2–), 70.5 (t, –OCH2–), 70.6 (t,
–OCH2–), 117.3 (s, 5-Pym-C), 160.7 (s, 2-Pym-C), 166.2 (s,
+
100) [M − (C8H17O2)2] , 135 (85). m/z (ESI, CHCl3) 1235
+
+
+
+
5%) [M2 + Na] , 629 (100) [M + Na] , 607 (15) [M + H] .
4-Pym-C, 6-Pym-C). m/z (EI, 70 eV) 283 (2%) [M] , 254 (6),
+
1
1
50 (99), 136 (100). m/z (CI, isobutane) 284 (100%) [M + H] ,
+
36 (17). m/z (ESI, CHCl3) 306 (8%) [M + Na] , 284 (100)
3
-Acetyl-6,9,12-trioxatetradecan-2-one (7)
+
[M + H] .
To a suspension of potassium tert-butoxide (14.6 g, 130 mmol)
in THF (100 mL) was added a solution of pentane-2,4-dione
13.0 g, 130 mmol) in THF (50 mL) at 0 C. To this mixture was
added a solution of 6, (18.6 g, 64.0 mmol) in THF (50 mL). The
reaction mixture was then heated to reflux for 18 h. After cool-
ing, the mixture was acidified with 1 N hydrochloric acid (pH 1)
and diluted with diethyl ether (200 mL). The layers were sep-
arated and the aqueous layer was extracted with diethyl ether
N,N’-Bis[4,6-dimethyl-5-(3,6,9-trioxaundecyl)-pyrimidin-
-yl]thiourea (9)
To a suspension of sodium bicarbonate (1.07 g, 12.7 mmol) and
(3.00 g, 10.6 mmol) in acetonitrile (50 mL) was added thio-
◦
(
2
8
phosgene (383 µL, 5.00 mmol) and the mixture was heated
to reflux for 18 h. After cooling, the solvent was evapo-
rated and the residue was purified by column chromatography
(
3 × 100 mL). The combined organic extracts were dried with
(
silica gel, DCM/ethanol (19/1), Rf = 0.31). Compound 9 was
magnesium sulfate and the solvent was removed under vacuum.
Column chromatography (silica gel, cyclohexane/ethyl acetate
−
1
obtained as a yellow oil (2.43 g, 80% yield). νmax (KBr)/cm
3
7
422, 2961, 2867, 1580, 1540, 1438, 1370, 1295, 1112,
91. δH (600 MHz, CDCl3, 25 C) 1.19 (6H, t, J 7.0, 11-
(
(
1/1), Rf 0.22) yielded 7 as a colourless oil (8.10 g, 47% yield).
Found C 59.56, H 9.52. Calcd for C13H24O5·0.1H2O: C 59.56,
◦
3
−
1
CH3), 2.53 (12H, s, 4-Pym-CH3, 6-Pym-CH3), 2.92 (4H, t,
H 9.31%.) νmax (film)/cm 3519, 2868, 1725, 1698, 1605,
3
J 6.7, 1-CH2), 3.51 (4H, q, 3J 7.0, 10-CH2), 3.55–3.64
◦
1
1
(
1
3
423, 1358, 1283, 1248, 1115, 848. δH (500 MHz, CDCl3, 25 C)
3
3
3
(20H, m, –OCH2–), 8.64 (1H, br s, NH), 13.75 (1H, br s,
.15 (3H, t, J 7.0, 14-CH3), 2.13 [1.2H, dt, J 6.9, J 5.9, 4-CH2
◦
†
†
NH). δC (150.9 MHz, CDCl3, 25 C) 15.1 (q, 11-CH3), 22.3
7a )], 2.17 [2.4H, s, 1-CH3, 3-C–COCH3 (7b )], 2.22 [3.6H, s,
-CH3, 3-CH–COCH3 (7a)], 2.55 [0.8H, t, J 7.3, 4-CH2 (7b)],
.46 [1.2H, t, J 5.9, 5-CH2 (7a)], 3.47 [0.8H, t, J 7.3, 5-CH2
3
(q, 4-Pym-CH3, 6-Pym-CH3), 28.6 (t, 1-CH2), 66.6 (t, 10-
CH2), 69.6 (t, 2-CH2), 69.8 (t, –OCH2–), 70.5 (t, –OCH2–),
70.7 (t, –OCH2–), 70.7 (t, –OCH2–), 166.8 (br s, 4-Pym-C, 6-
Pym-C), 177.8 (s, C=S). Signals for 2-Pym-C and 5-Pym-C
could not be observed. m/z (EI, 70 eV) 457 (18%), 136 (100).
m/z (CI, isobutane) 326 (16%), 284 (100), 135 (85). m/z (ESI,
3
3
3
(
3
7b)], 3.53 (2H, q, J 7.0, 13-CH2), 3.57–3.67 (8H, m, –OCH2–),
3
.86 [0.6H, t, J 6.9, 3-CH (7a)]. Signal for the enol proton could
◦
not be observed. δC (125.8 MHz, CDCl3, 25 C) 15.0 (q, 14-
CH3), 23.0 [q, 1-CH3, 3-C–COCH3 (7b)], 27.8 [t, 4-CH2 (7b)],
8.2 [t, 4-CH2 (7a)], 29.3 [q, 1-CH3, 3-CH–COCH3 (7a)], 65.4
d, 3-CH (7a)], 66.5 (t, 13-CH2), 68.5 [t, 5-CH2 (7a)], 68.6 [t,
-CH2 (7b)], 69.6 (t, –OCH2–), 70.0 (t, –OCH2–), 70.3 (t, –
+
+
CHCl3) 631 (100%) [M + Na] , 609 (30) [M + H] . (Found
2
[
5
+
6
31.3239. Calcd for C29H48N6O6SNa : 631.3254 (2.4 ppm);
Found 632.3346. Calcd for C28 CH48N6O6SNa : 632.3287
9.3 ppm).)
13
+
(
OCH2–), 70.5 (t, –OCH2–), 106.6 [s, 3-C (7b)], 191.6 [s, C=O
+
(
(
[
7b)], 204.1 [s, C=O (7a)]. m/z (EI, 70 eV) 260 (2%) [M] , 161
6), 127 (63), 85 (100), 73 (85). m/z (CI, isobutane) 261 (23%)
Acknowledgement
+
+
M + H] , 127 (40). m/z (ESI, CHCl3) 283 (100%) [M + Na] .
The support of the Deutsche Forschungsgemeinschaft (Lu 378/15) is
gratefully acknowledged.
GC tret = 15.5 min, purity: 96%.
2
-Amino-4,6-dimethyl-5-(3,6,9-trioxaundecyl)-
References
pyrimidine (8)
[
1] (a) J.-M. Lehn, Supramolecular Chemistry: Concepts and Perspec-
tives 1995 (Wiley-VCH: Weinheim).
Under a N2 atmosphere, sodium (920 mg, 40.0 mmol) was
carefully dissolved in 100 mL of anhydrous ethanol to give a
sodium ethanolate solution. To this solution was added guani-
dine hydrochloride (3.82 g, 40.0 mmol), and the mixture was
stirred for 15 min at RT, the solid was filtered off and the solvent
was evaporated. The residue was dissolved in THF (100 mL), 7
(b) J. W. Steed, J. L.Atwood, Supramolecular Chemistry 2000 (Wiley-
VCH: New York, NY).
(c) G. R. Desiraju, Encyclopedia of Supramolecular Chemistry 2004,
p. 658 (Marcel Dekker Inc: New York, NY).
[
2] (a) S. C. Zimmerman, P. S. Corbin, Struct. Bond. 2000, 96, 63.
doi:10.1007/3-540-46591-X_3
(
7.72 g, 29.7 mmol) was added, and the solution was heated to
(
b) G. Cooke, V. M. Rotello, Chem. Soc. Rev. 2002, 31, 275.
reflux for 18 h.After cooling, the solvent was evaporated and the
residue was dissolved in DCM (50 mL) and water (50 mL). The
layers were separated and the aqueous layer was extracted with
DCM (3 × 50 mL). The combined organic extracts were dried
with magnesium sulfate and the solvent was removed under vac-
uum. Column chromatography (silica gel, DCM/ethanol (9/1),
Rf 0.24) yielded 8 as a colourless solid (3.30 g, 40% yield).
doi:10.1039/B103906G
[
3] (a) R. C. Haworth, F. G. Mann, J. Chem. Soc. 1943, 603.
doi:10.1039/JR9430000603
(
b) R. Bunnenberg, J. C. Jochims, Chem. Ber. 1981, 114, 2075.
doi:10.1002/CBER.19811140609
(c) B. Akteries, J. C. Jochims, Chem. Ber. 1986, 119, 83.
doi:10.1002/CBER.19861190109
◦
[4] D. Meshcheryakov, F. Arnaud-Neu, V. Böhmer, M. Bolte, J. Cavaleri,
Mp 34.3–34.8 C. (Found C 59.28, H 9.18, N 14.89. Calcd for
−
1
V. Hubscher-Bruder, I.Thondorf, S.Werner, Org. Biomol. Chem. 2008,
C14H25N3O3: C 59.34, H 8.89, N 14.83%.) νmax (KBr)/cm
346, 3192, 2869, 1637, 1561, 1466, 1388, 1240, 1111, 798, 559.
6, 3244. doi:10.1039/B808773C
3
[
5] (a) S. J. Brooks, P. A. Gale, M. E. Light, CrystEngComm 2005, 7, 586.
◦
3
δH (500 MHz, CDCl3, 25 C) 1.16 (3 H, t, J 7.0, 11-CH3), 2.30
doi:10.1039/B511932D
3
(
6H, s, 4-Pym-CH3, 6-Pym-CH3), 2.77 (2H, t, J 7.5, 2-CH2),
(
2
b) S. J. Brooks, P. R. Edwards, P. A. Gale, M. E. Light, N. J. Chem.
006, 30, 65. doi:10.1039/B511963D
3
3
3
3
.46 (2H, t, J 7.5, 1-CH2), 3.47 (2H, q, J 7.0, 10-CH2), 3.54–
.64 (8H, m, –OCH2–), 5.19 (2H, br s, NH2). δC (125.8 MHz,
[
6] R. P. Sijbesma, F. H. Beijer, L. Brunsveld, B. J. B. Folmer,
J. H. K. K. Hirschberg, R. F. M. Lange, J. K. L. Lowe, E. W. Meijer,
Science 1997, 278, 1601. doi:10.1126/SCIENCE.278.5343.1601
◦
CDCl3, 25 C) 15.0 (q, 11-CH3), 21.8 (q, 4-Pym-CH3, 6-Pym-
CH3), 28.0 (t, 1-CH2), 66.5 (t, 10-CH2), 69.7 (t, 2-CH2), 70.0