Tertiary alcohols based on 1-acetylpyrene

Article abstract of DOI:10.1134/S1070428007100144

From 1-acetylpyrene by reactions with butyllithium, lithium alkylacetylenides and peroxyacetylenides previously unknown teritary alcohols were synthesized.

Full text of DOI:10.1134/S1070428007100144

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 10, pp. 1492−1494. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © E.A. Dikusar, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 10, pp. 1499−1501.
Tertiary Alcohols Based on 1-Acetylpyrene
E. A. Dikusar
Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus, Minsk, 220072 Belarus
e-mail: evgen_58@mail.ru
Received April 10, 2006
Abstract—From 1-acetylpyrene by reactions with butyllithium, lithium alkylacetylenides and peroxyacetylenides
previously unknown tertiary alcohols were synthesized.
DOI: 10.1134/S1070428007100144
A convenient procedure for preparation peroxy group
containing tertiary acetylene alcohols by treating with
lithium peroxyacetylenides 1-and 2-acetonaphthone was
formerly described [1,2].
alcohols II–VIII was confirmed by elemental analysis,
molecular weight measurement by cryoscopy, UV,
1H NMR, and IR spectroscopy. The spectral data are in
good agreement with the data published for related
compounds [3]. The purity of compounds obtained was
95 1% according to 1H NMR spectra.
O
HO
R
Me
Me
(1) RLi
(2) H2O
EXPERIMENTAL
IR spectra were recorded on a Fourier spectro-
photometer Protege-460 (Nicolet) from thin films. UV
spectra were measured on a spectrophotometer Specord
UV Vis from solutions of compounds in methanol of
concentration 1×10–4 M. 1H NMR spectra were registered
on a spectrometer Tesla BS-587A (100 MHz) from 5%
solutions in CDCl3, chemical shifts were measured from
internal reference TMS. Molecular weights were
measured by cryoscopy in benzene. Column chromato-
graphy was carried out on neutral aluminum oxide L 40/
250 μm of II grade Brockmann activity (eluent hexane–
ethyl ether mixture).
_
I
II VIII
R = Bu (II), C≡C(CH2)4Me (III), C≡C(CH2)15Me (IV),
C≡CCMe2OOCMe3 (V), C≡CCMe2OOCMe2Et (VI),
C≡CCMe2OOCMe2Pr (VII), C≡CCMe2OOCMe2C6H5
(VIII).
In this study a preparative synthesis was carried out
of previously unknown tertiary alcohols II–VIII by
treating 1-acetylpyrene (I) with butyllithium, lithium
alkylacetylenides and peroxyacetylenides obtained by
reacting butyllithium with the corresponding monosub-
stituted alkynes and peroxyalkynes [2]. The tertiary
alcohols containing in their structure alongside the
aromatic pyrene fragment also acetylene (III–VIII) and
peroxy (V–VIII) groups were synthesized in 80–90%
yields. They were purified by column chromatography
on aluminum oxide. Compounds II–VIII are yellow
viscous pasty substances well soluble in common organic
solvents and insoluble in water. We failed to obtain
compounds II–VIII in the crystalline state. They are
stable at storage at 0–5°C in the dark. The structure of
1-Acetylpyrene (I) used was of 97% purity, mp 86–
89°C [3]. Initial peroxyalkynes and butyllithium were
prepared by procedures [4] and [5] respectively.
Tertiary alcohols based on 1-acetylpyrene II–VIII.
To a solution of 5.5 mmol of butyllithium (or lithium
alkylacetylenide or lithium peroxyacetylenides obtained
by reacting butyllithium with the corresponding
monosubstituted alkynes and peroxyalkynes) in 50 ml
of benzene mixture with anhydrous ethyl ether cooled to
–20°C was added under argon atmosphere in one portion
at vigorous stirring 4 mmol of 1-acetylpyrene (I). The
reaction temperature was slowly raised to 20–23°C, and
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TERTIARY ALCOHOLS BASED ON 1-ACETYLPYRENE
1493
the stirring was continued for 2–3 h till complete
dissolution of the crystals of compound I. The reaction
mixture was left standing for 15–20 h at 20–23°C, then
it was diluted with 100 ml of hexane and washed with
water 3–4 times. The organic layer was separated and
dried over CaCl2. The solvent was removed, and the
residue was kept under a vacuum. Tertiary alcohols II–
VIII were purified by column chromatography on
aluminum oxide.
(OH), 3115, 3090, 3040 (CHAr), 2979, 2931, 2865
(CHAlk), 1630, 1600, 1580, 1510, 1375, 1362, 1247 (Ar),
1154, 1082 (C–O), 867 (O–O), 847, 827, 819, 760, 723,
683 (CHAr). UV spectrum , λmax, nm (ε): 204 (25000),
209 (18000), 233 (45000), 243 (70000), 255 (15000),
265 (28000), 277 (50000), 300 (6000), 313 (13000), 328
1
(30000), 345 (48000). H NMR spectrum, δ, ppm:
1.23 s (9H, Me3COO), 1.49 s (6H, Me2C), 2.13 s (3H,
Me), 2.74 s (1H, OH), 7.85–9.15 m (9Harom). Found, %:
C 81.16; H 7.19. M 388.2. C27H28O3. Calculated, %:
C 80.97; H 7.05. M 400.5.
2-(1-Pyrenyl-2-hexanol) (II). Yield 80%. IR
spectrum, ν, cm–1: 3440 (OH), 3115, 3090, 3040 (CHAr),
2955, 2929, 2869 (CHAlk), 1625, 1595, 1584, 1540, 1507,
1383, 1253, 1231 (Ar), 1131 (C–O), 848, 820, 758, 721,
684, 670, 635 (CHAr). UV spectrum , λmax, nm (ε): 204
(26000), 209 (18000), 233 (42000), 243 (70000), 255
(14000), 265 (28000), 277 (49000), 313 (13000), 328
(30000), 343 (47000). 1H NMR spectrum, δ, ppm: 0.73
t (3H, Me), 1.00–1.35 m [4H, (CH2)2], 1.86 s (3H, Me),
2.15 q (2H, CH2), 2.90 s (1H, OH), 7.60–9.05 m (9Harom).
Found, %: C 87.64; H 7.45. M 290.7. C22H22O.
Calculated, %: C 87.28; H 7.33. M 302.4.
5-Methyl-5-tert-pentylperoxy-2-(1-pyrenyl)-3-
hexyn-2-ol (VI). Yield 84%. IR spectrum, ν, cm–1: 3420
(OH), 3115, 3090, 3041 (CHAr), 2981, 2935, 2869
(CHAlk), 1630, 1600, 1580, 1510, 1376, 1363, 1247 (Ar),
1461 (CH2), 1154, 1083 (C–O), 865 (O–O), 848, 826,
820, 761, 723, 682 (CHAr). UV spectrum , λmax, nm (ε):
204 (25000), 210 (18000), 233 (44000), 243 (70000),
255 (15000), 265 (28000), 277 (50000), 300 (5000), 313
(13000), 328 (30000), 345 (48000). 1H NMR spectrum,
δ, ppm: 0.90 t (3H, Me), 1.11 s (6H, Me2COO), 1.42 q
(2H, CH2), 1.45 s (6H, CH2), 2.08 s (3H, Me), 2.88 s
(1H, OH), 7.65–9.07 m (9Harom). Found, %: C 81.45;
H 7.42. M 403.6. C28H30O3. Calculated, %: C 81.13;
H 7.29. M 414.5.
2-(1-Pyrenyl)-3-nonyn-2-ol (III). Yield 84%. IR
spectrum, ν, cm–1: 3420 (OH), 3115, 3092, 3040 (CHAr),
2955, 2930, 2870, 2860 (CHAlk), 2240 (C≡C), 1625,
1595, 1580, 1510, 1380, 1255, 1231 (Ar), 1460 (CH2),
1083 (C–O), 844, 820, 760, 720, 684 (CHAr). UV
spectrum , λmax, nm (ε): 204 (25000), 209 (18000), 233
(43000), 243 (70000), 255 (14000), 265 (28000), 277
(50000), 300 (6000), 313 (13000), 328 (30000), 343
5-Methyl-5-(2-methyl-2-pentylperoxy)-2-(1-
pyrenyl)-3-hexyn-2-ol (VII). Yield 90%. IR spectrum,
ν, cm–1: 3405 (OH), 3115, 3090, 3040 (CHAr), 2983,
2959, 2935, 2871 (CHAlk), 1630, 1598, 1580, 1510, 1377,
1362, 1249 (Ar), 1460 (CH2), 1153, 1083 (C–O), 865
(O–O), 849, 828, 760, 724, 684 (CHAr). UV spectrum ,
1
(47000). H NMR spectrum, δ, ppm: 0.74 t (3H, Me),
1.00–1.65 m [6H, (CH2)3], 2.04 s (3H, Me), 2.15 q (2H,
CH2), 2.95 s (1H, OH), 7.45–9.05 m (9Harom). Found,
%: C 88.67; H 7.35. M 324.4. C25H24O. Calculated, %:
C 88.20; H 7.10. M 340.5.
λ
max, nm (ε): 204 (24000), 210 (18000), 233 (44000),
243 (70000), 255 (15000), 265 (28000), 277 (50000),
300 (6000), 313 (13000), 328 (30000), 345 (48000). 1H
NMR spectrum, δ, ppm: 0.89 t (3H, Me), 1.15 s (6H,
Me2COO), 1.25–1.55 m [4H, (CH2)2], 1.45 s (6H, CH2),
2.07 s (3H, Me), 2.92 s (1H, OH), 7.65–9.07 m (9Harom).
Found, %: C 81.70; H 7.61. M 410.3. C29H32O3.
Calculated, %: C 81.27; H 7.53. M 428.6.
2-(1-Pyrenyl)-3-eicosyn-2-ol (IV). Yield 85%. IR
spectrum, ν, cm–1: 3420 (OH), 3114, 3087, 3041 (CHAr),
2924, 2852 (CHAlk), 2240 (C≡C), 1620, 1594, 1580,
1510, 1383, 1253, 1231 (Ar), 1465 (CH2), 1085 (C–O),
846, 830, 820, 760, 721, 682 (CHAr). UV spectrum , λmax
,
nm (ε): 205 (24000), 209 (18000), 233 (42000), 243
(70000), 255 (13000), 265 (27000), 277 (50000), 300
(6000), 313 (12000), 328 (30000), 343 (46000). 1H NMR
spectrum, δ, ppm: 0.86 t (3H, Me), 1.05–2.65 m [28H,
(CH2)14], 2.13 s (3H, Me), 2.18 q (2H, CH2), 2.75 s (1H,
OH), 7.75–9.20 m (9Harom). Found, %: C 87.85; H 9.42.
M 481.9. C36H46O. Calculated, %: C 87.40; H 9.37.
M 494.8.
5-Methyl-2-(1-pyrenyl)-5-(2-phenylprop-2-
ylperoxy)-3-hexyn-2-ol (VIII). Yield 86%. IR spectrum,
ν, cm–1: 3420 (OH), 3112, 3090, 3065, 3040, 3030, 3012
(CHAr), 2983, 2933, 2870 (CHAlk), 1630, 1605, 1590,
1447, 1515, 1377, 1360, 1253 (Ar), 1151, 1083 (C–O),
862 (O–O), 849, 820, 762, 720, 699, 680 (CHAr). UV
spectrum , λmax, nm (ε): 205 (31000), 210 (20000), 234
(43000), 244 (70000), 255 (14000), 265 (28000), 277
(50000), 300 (6000), 314 (13000), 328 (30000), 343
5-tert-Butylperoxy-5-methyl-2-(1-pyrenyl)-3-
hexyn-2-ol (V). Yield 82%. IR spectrum, ν, cm–1: 3422
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 10 2007

DIKUSAR
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1
(48000). H NMR spectrum, δ, ppm: 1.45 s (6H,
Me2COO), 1.49 s (6H, Me2C), 2.12 s (3H, Me), 2.78 s
(1H, OH), 7.00–9.12 m (14H, Ar). Found, %: C 83.38;
H 6.55. M 449.0. C32H30O3. Calculated, %: C 83.09;
H 6.54. M 462.6.
Moiseichuk, K.L., Isakovich, O.I., and Yuvchenko, A.P.,
Zh. Obshch. Khim., 2003, vol. 73, p. 620.
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4. Yuvchenko, A.P., Moiseichuk, K.L., Dikusar, Yu.A., and
Ol’dekop, Yu.A., Vestsi Akad. Nauk Belarusi, Ser.Khim.
Nauk, 1995, no. 2, p. 65.
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organicheskoi khimii. Litii, natrii, kalii, rubidii, tsezii
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 10 2007