Thermolysis of 3-(1-adamantyl)-2-hydroxy-5-methylbenzyl-(trimethyl)ammonium iodide

Full text of DOI:10.1134/S1070428011060248

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 6, pp. 958–959. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © V.A. Osyanin, Yu.V. Popova, Yu.N. Klimochkin, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 6,
pp. 939–940.
SHORT
COMMUNICATIONS
Thermolysis of 3-(1-Adamantyl)-2-hydroxy-5-methylbenzyl-
(trimethyl)ammonium Iodide
V. A. Osyanin, Yu. V. Popova, and Yu. N. Klimochkin
Samara State Technical University, ul. Molodogvardeiskaya 244, Samara, 443100 Russia
e-mail: orgchem@samgtu.ru
Received March 22, 2010
DOI: 10.1134/S1070428011060248
In the absence of nucleophiles and dienophiles
o-quinomethanes undergo fast oligomerization with
formation of a complex mixture of products as a result
of hetero-Diels–Alder reaction with opposite electronic
requirements. In some cases, the corresponding trimer-
ization product can be isolated as the major one. Here,
initial o-quinomethanes were generated in situ by
oxidation of o-alkylphenols with Ag2O or K3[Fe(CN)6]
[1], from unstable o-halomethylphenols [2], difficultly
accessible enediynes [3] and 4-alkynylcyclobutenones
[4], as well as by flash vacuum pyrolysis of salicyl
alcohols, o-methoxymethylphenols [5], and 4H-1,3,2-
benzodioxaborinines [6].
We have found that heating of sterically hindered
3-(1-adamantyl)-2-hydroxy-5-methylbenzyl(trimethyl)-
ammonium iodide (I) in boiling dimethylformamide
leads to the formation of formal trimerization product
of the corresponding o-quinomethane A via tandem
[4+2]-cycloaddition.
1
The H NMR spectrum of trimer II contained a set
of singlets in the region δ 6.66–6.96 ppm from aro-
matic protons and signals from protons in the adaman-
tane fragments at δ 1.56–2.30 ppm. The vinylic proton
resonated as a singlet at δ 6.16 ppm, and methylene
protons in the Carom–CH2–CH fragment gave doublets
of doublets at δ 2.93 and 3.23 ppm. In the IR spectrum
OH
O
A
DMF, 153°C
CH2
O
NMe3
–Me3N·HI
O
I–
Me
Me
Me
Me
I
A
B
Me
O
A
O
O
Me
Me
II
958

THERMOLYSIS OF 3-(1-ADAMANTYL)-2-HYDROXY-5-METHYLBENZYL-...
959
of II, absorption band corresponding to the conjugated
carbonyl group was observed at 1697 cm–1. The base
peak in the mass spectrum of II belonged to adamantyl
cation.
CH), 2.93 d.d and 3.24 d.d (1H each, 9′-H), 6.16 s (1H,
=CH), 6.66 s (1H, Harom), 6.72 s (1H, Harom), 6.89 s
(1H, Harom), 6.96 s (1H, Harom). Mass spectrum, m/z
(Irel, %): 762 (3) [M]+, 747 (1) [M – Me]+, 627 (2) [M –
C10H15]+, 508 (15) [C36H44O2]+, 507 (14) [C36H43O2]+,
506 (11) [C36H42O2]+, 494 (7), 493 (4), 373 (3)
[C26H29O2]+, 256 (12), 255 (24), 254 (7) [C18H22O]+,
253 (11), 242 (5), 199 (6), 185 (5), 159 (5), 135 (100)
[C10H15]+, 107 (7), 93 (12), 79 (11), 67 (6). Found, %:
C 85.08; H 8.68. C54H66O3. Calculated, %: C 84.99;
H 8.72.
Initial iodide I was synthesized by aminomethyla-
tion of 2-(1-adamantyl)-4-methylphenol in ethanol,
followed by quaternization with methyl iodide [7].
3-(1-Adamantyl)-2-hydroxy-5-methylbenzyl(tri-
methyl)ammonium iodide (I). 2-(1-Adamantyl)-4-
methylphenol, 5 g (0.021 mol), was dissolved in 30 ml
of ethanol, 3.5 g (0.026 mol) of 33% aqueous dimeth-
ylamine and 2.6 g (0.026 mol) of 30% aqueous formal-
dehyde were added, and the mixture was kept for
2 days at room temperature and then for 2 h at –20°C.
The colorless precipitate was filtered off, washed with
ice-cold methanol, and dried in air. A mixture of the
Mannich base thus obtained and 20 ml of methyl
iodide was heated for 12 h under reflux with stirring.
The mixture was cooled, and the colorless precipitate
was filtered off and washed with ice-cold diethyl ether.
Yield 5.5 g (60%), mp 217–219°C. IR spectrum, ν,
cm–1: 3387, 3190 (OH); 2901, 2847 (CH, Ad); 1609
(C=C); 1462, 1269, 1211, 1180, 1011, 872, 756.
1H NMR spectrum (DMSO-d6), δ, ppm: 1.70 s (6H,
Ad), 2.01 s (3H, Ad), 2.05 s (6H, Ad), 2.22 s (3H,
CH3), 2.95 s (9H, NMe3), 4.49 s (2H, CH2), 7.00 s (1H,
Harom), 7.08 s (1H, Harom), 8.59 s (1H, OH). Found, %:
C 56.98; H 7.29. C21H32INO. Calculated, %: C 57.08;
H 7.25.
The IR spectra were measured in KBr on
a Shimadzu FTIR-8400S spectrometer. The 1H NMR
spectra were recorded on a Bruker AM-400 spectrom-
eter at 400 MHz using tetramethylsilane as internal
reference. The mass spectrum (electron impact, 70 eV)
was obtained on a Finnigan Trace DSQ instrument.
The elemental compositions were determined on
a EuroVector EA-3000 automatic CHNS analyzer.
This study was performed under financial support
by the Council for Grants at the President of the
Russian Federation (program for state support of
young Russian scientists, project no. MK-3368.2011.3)
with the use of facilities provided by the special-pur-
pose integrated program “Studies on Physicochemical
Properties of Substances and Materials.”
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1
984, 945. H NMR spectrum (CDCl3), δ, ppm: 1.56–
1.64 m (9H, Ad, 4a′-CH3), 1.75–1.85 m (15H, Ad),
1.88–1.97 m (6H, Ad), 2.07–2.19 m (12H, Ad), 2.21–
2.30 m (12H, Ad, CH3), 2.44–2.73 m (5H, CH2CH2,
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 6 2011