Chemical Transformations of Tetracyclo[3.3.1.1.3,7.0.1,3]decane (1,3-Dehydroadamantane): VIII. Reaction of 1,3-Dehydroadamantane with Aliphatic Aldehydes

Article abstract of DOI:10.1134/S1070428019050099

The reaction of 1,3-dehydroadamantane with aliphatic aldehydes involves the C^a-H bond and forms hardly accessible branched 2-(1-adamantyl)alkylaldehydes in one stage in a yield of 60-78%. It is found that 2-(1-adamantyl)alkylaldehydes are prone

Full text of DOI:10.1134/S1070428019050099

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2019, Vol. 55, No. 5, pp. 640–645. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Zhurnal Organicheskoi Khimii, 2019, Vol. 55, No. 5, pp. 737–742.
Chemical Transformations of Tetracyclo[3.3.1.1.3,7.0.1,3]decane
(1,3-Dehydroadamantane):
VIII1. Reaction of 1,3-Dehydroadamantane
with Aliphatic Aldehydes
V. M. Mokhova,*, K. R. Saadb, G. Yu. Parshina, and G. M. Butova,b,**
a Volgograd State Technical University, pr. Lenina 28b, Volgograd, 400131 Russia
*e-mail: tons@vstu.ru
b Volzhsky Polytechnic Institute (Branch), Volgograd State Technical University,
ul. Engelsa 42, Volzhskii, Volgograd obl., 404121 Russia
**e-mail: butov@post.volpi.ru
Received May 16, 2018; revised February 10, 2019; accepted February 11, 2019
Abstract—The reaction of 1,3-dehydroadamantane with aliphatic aldehydes involves the Сα-Н bond and
forms hardly accessible branched 2-(1-adamantyl)alkylaldehydes in one stage in a yield of 60–78%. It is found
that 2-(1-adamantyl)alkylaldehydes are prone to oligomerization. The reaction of 2-(1-adamantyl)-
alkylaldehydes with 2,4-dinitrophenylhydrazine gave the corresponding hydrazones in a yield of 84–98%.
Keywords: propellanes, 1,3-dehydroadamantane, aldehydes, hydrazones
DOI: 10.1134/S1070428019050099
Adamantyl-substituted aldehydes are valuable
synthons for the synthesis of amines and other
physiologically active compounds [2–4]. The synthesis
of such aldehydes is complicated and multistage and
often leads to low yields. Therefore, the diversity of
known adamantyl-substituted aldehydes is not so wide
and mainly includes structures with unbranched
aliphatic spacers between the adamantan-1-yl and
aldehyde groups.
tanecarbonitriles followed by in situ hydrolysis [4].
The same conditions were used to prepare 3-
(adamantan-1-yl)propanal [4]. However, the synthesis
of the starting adamantan-1-ylcarbonitriles is
infrequently complicated and multistage.
Kell and McQuill [6] synthesized adamantan-1-
ylacetaldehyde from adamantan-1-ol and acetylene in
sulfuric acid, but the reaction was accompanied by the
formation of a large quantity of 1-methylhomoada-
mantan-2-one as a by-product.
The best documented is the synthesis of the
simplest representative of this class of compounds,
adamantan-1-ylcarbaldehyde 1-AdC(O)H. One of the
synthetic approaches consists in the decomposition of
N-(tert-butyl)adamantane-1-ylaziridine with mineral
acids [5]. However, the initial aziridine is difficult to
synthesize. Another synthesis 1-AdC(O)H involves
passing a stream of CO through a mixture of adaman-
tane, methylene chloride, and aluminum chloride at 0°
C; the yield of the target product is 49% [3].
Adamantan-1-alkanals are most frequently prepared
by the oxidation of the corresponding adamantan-1-
ylalkanols with lead tetraacetate or hydrolysis of the
corresponding diacetals prepared by the reaction of
orthoformic ester with Grignard reagents. The yields of
these two syntheses are close to each other (37‒57%)
[2]. However, when reduced to the starting
adamantane, including the synthesis of the starting
compounds, the yield of adamantan-1-alkanales is as
low as 12%.
Adamantan-1-ylcarbaldehyde was also prepared in
a yield of up 91% by the Stephen reduction of adaman-
The above-described reactions all relate to the
synthesis of linear adamantan-1-ylalkanals. The
1
For communication VII, see [1].
640

CHEMICAL TRANSFORMATIONS OF TETRACYCLO[3.3.1.1.3,7.0.1,3]DECANE
641
Scheme 1.
O
O
OH
O
O
RCHO
+
R
R
R
R
R
O
O
RCHO
R
R
O
O
H
+
R
R
synthesis of branched adamantan-1-ylalkanals has
been scarcely reported. Buckle et al. [7] described the
synthesis of 2-(adamantan-1-yl)propanal by the
reaction of 2-(adamantan-1-yl)propanoic acid with
oxalyl chloride in dichloromethane, yielding the
corresponding chloride, and subsequent Pd-catalyzed
hydrogenation of the latter.
It should be noted that propellane 1 can attack not
only the activated α-CH bond of the methylene group
in aldehydes, which is sterically more accessible than
in ketones, but also the С(О)‒Н bond, which is lacking
in ketones. This difference in the structure of the
substrates can affect the selectivity of the reaction and
forms not only aldehydes, but also adamantyl-
substituted ketones. Wiberg and Waddell [14]
observed formation of a complex mixture of products
in reactions between [1.1.1]propellane and aldehydes
and proposed a radical mechanism of these reactions to
explain the obtain result (Scheme 1).
1,3-Dehydroadamantane (1,3-DHA, propellane 1)
reacts by the activated Сα‒Н bond in carbonyl [8] and
dicarbonyl compounds [9] to form in high yields and
in one stage hardly accessible cyclic and aromatic
ketones and diketones containing an α-adamantan-1-yl
group and also alkylate the Сα‒Н bond in carboxylic
acid derivatives: nitriles [10], amides [11], and esters
[12].
As the starting reagents in the reaction with
propellane 1 we used propanal 2a, pentanal 2b,
hexanal 2c, and 2-methylpropanal 2d. First we focused
on the reaction of propellane 1 with aldehydes 2a‒2d
in the absence of a solvent and catalyst, and with an
excess of the starting aldehydes (ratio 1 : 5) in a dry
oxygen-free nitrogen atmosphere (Scheme 2).
The Сα‒Н protons in aldehydes are more mobile
than in ketones, and, therefore, we expected that
aldehydes would more actively react with propellane 1
than the corresponding ketones. Thus, the dissociation
ketones рKа of aldehydes in water are 14‒18, whereas
the respective рKа values for ketones are 19‒20 [13].
These data allowed us to expect that propellane 1
would react by the Сα‒Н bond in aliphatic aldehydes to
form aldehydes containing the adamantan-1-yl group
in the α position. This reaction would allow synthesis
of aldehydes with branched spacers between the
adamantan-1-yl and aldehyde groups, which are either
impossible to synthesize by other methods or their
synthesis involves many stages and makes use of
costly and flammable reagents.
The reaction was performed in mild conditions (40‒
60°С) for 2‒3 h. The reaction progress was monitored
by GC–MS. Compounds 3a‒3d were isolated vacuum
distillation of the residue left after removal of the
starting aldehydes. The yield of aldehydes 3a‒3d was
60‒78%.
It was shown that main reaction products are
aldehydes 3a‒3d. The absence of ketones, which could
be formed by the reaction of propellane 1 by the С(О)‒Н
group, suggests a non-radical mechanism of the
reaction, where aliphatic aldehydes 2a‒2d act as СН
Scheme 2.
R2
R2
R1
CHO
+
CHO
H
R1
2a_d
3a_d
1
R1 = H, R2 = Me (2a, 3a), Pr (2b, 3b), Bu (2c, 3c); R1 = R2 = Me (2d, 3d).
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MOKHOV et al.
642
acids. Thus, propellane 1 differs in chemical behavior
from [1.1.1]propellane.
The reaction of propellane 1 with propanal 2a
proved to be sensitive to the polarity of the solvent.
The reactions in hexane (35‒40°С) or diethyl ether
(under reflux) failed: traces of aldehyde 3а and the
starting reagents were identified in the reaction
mixtures. Even though the reaction time was prolonged
to 6 h or the reaction temperature was increased to 68°С,
no aldehyde 3a formed. It was therefore was conclu-
ded that the result of the reaction with propellane 1 is
strongly dependent on the Сα‒Н polarization in the
starting aliphatic aldehydes. As known [17], СН
acidity depends on the polarity of the solvent.
Apparently, the apolar hexane and weakly polar
diethyl ether do not favor polarization of the Сα‒Н
bond in propanal 2a and its acidity, thereby strongly
decreasing the reaction rate and yield of aldehyde 3а.
Aldehydes 3a‒3d are colorless high-boiling liquids
with a characteristic odor. Their structure and compo-
sition were confirmed by IR spectroscopy, GCMS, and
elemental analysis.
The IR spectra of compounds 3a‒3d display
absorption bands at 1725‒1730 cm–1 assignable to
stretching vibrations of the aldehyde C=O group [15].
Absorption bands characteristic of the adamantane
С‒Н bonds are also observed in different spectral
regions (1364, 1450‒1485, and 2840‒2956 cm–1 [16]).
The mass spectra of aldehydes 3a‒3d contain weak
peaks of the molecular ions and [M ‒ CO] ions, as well
as an adamantly ion peak at m/z 135 (100%).
Aldehydes 3a‒3d, notwithstanding their branched
spacer and steric hindrances, undergo oligomerization
on storage (1‒9 days). 2-(Adamantan-1-yl)propanal 2a
is liquid at room temperature, but it gradually
transforms into a crystalline material, the melting point
of which gradually increases from 64 to 130°С within
the next few days. The carbonyl absorption band in the
IR spectra of the oligomeric aldehydes substantially
attenuates compared to that in the spectra of the
starting aldehydes 3a‒3d. Earlier Stepanov and
Dovgan’ [2] noticed a high tendency for spontaneous
oligomerization of 1-АdC(O)H, which was lower in 2-
(adamantan-1-yl)-ethanal and absent in 3-(adamantan-
1-yl)propanal [2].
To study the effect of reaction conditions on the
selectivity of formation and yield of the target
aldehyde, we reacted propellane 1 with propanal 2a at
varied temperatures, reagent ratios, and solvents. The
yield of aldehyde 3a increased from 35 to 74%, when
the reaction temperature was increased from 20 to
40°C, 1 : 2а ratio to 1 : 5, and reaction time to 3 h.
Further increase of the temperature to 65°С decreases
the selectivity and yield of compound 3a to 42%.
Prolong heating of the reaction mixture (6‒9 h) leads
to the formation of high-boiling by-products. It was
suggested that this result is explained by aldol
condensation. Evidence for this suggestion was
obtained by GCMS analysis. For example, among the
products of the reaction of propellane 1 with pentanal
2b we detected, along with aldehyde 3b, a compound
that gives a molecular ion peak at m/z 306. This
compound was identified as the product of the aldol
condensation of aldehyde 3b with pentanal 2b.
In view of the spontaneous oligomerization, for
reliable structural assessment of the synthesized
compounds we performed a test for the carbonyl
group, specifically, the reaction of aldehydes 3a‒3d
with 2,4-dinitrophenylhydrazine 4. The reaction was
performed by a standard procedure [18] in ethanol in
the presence of an acid catalyst at a 1 : 1.2 molar ratio
of aldehyde 3a–3d and hydrazine 4 at 25°С for
15‒20 min immediately after the isolation of aldehydes
3a‒3d (Scheme 3).
Changing the 1 : 2a molar ratio from 1 : 2 to 1 : 6 at
40°С and the reaction time to 3 h increased the yield of
aldehyde 3a from 64 to 76%. When the 1 : 2a ratio was
1 : 2, other conditions being equal, along with aldehyde
3a, some starting propellane 1 was recovered.
Scheme 3.
O2N
O2N
R2
3a_3d
H2NHN
NO2
+
CH
N
NH
NO2
R1
4
5a_5d
R1 = H, R2 = Me (3a, 5a), Pr (3b, 5b), Bu (3c, 5c); R1 = R2 = Me (3d, 5d).
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CHEMICAL TRANSFORMATIONS OF TETRACYCLO[3.3.1.1.3,7.0.1,3]DECANE
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The yields of hydrazones 5a‒5d were 84–98%.
After completion of the reaction, hydrazones 5a‒5d
were filtered off and recrystallized from aqueous
alcohol. Hydrazones 5a‒5d are bright yellow crystals.
temperature was ramped from 80 to 280°С, injector
temperature 250°С. The H NMR spectra of dinitro-
1
phenylhydrazones 5a‒5d were measured on Bruker
DRX 500 (500.13 MHz) and Varian Mercury-300
spectrometers (300 MHz) in DMSO-d6 against internal
TMS. Elemental analysis was performed on a Perkin-
Elmer Series II 2400 analyzer.
1
Their composition and structure was confirmed by Н
NMR spectroscopy, mass spectrometry, and elemental
analysis. The mass spectra of hydrazones 5a‒5d
display weak molecular ion peaks (1‒8%). The spectra
of hydrazones 5a‒5d all characteristically show strong
peaks of the adamantyl ion at m/z 135. These peaks are
base peaks in the mass spectra of hydrazones 5a and
5с. The base peaks in the mass spectra of hydrazones
5b and 5d are those formed by the fragment ions of the
adamantane core at m/z 41 [11], while the intensity of
the adamantly ion peak is no higher than 22%.
2-(Adamantan-1-yl)propanal (3a). A mixture of 9 g
(0.15 mol) of propanal 2а and 4 g (0.03 mol) of
propellane 1 was heated at 35‒40°С for 3 h, after
which excess propanal 2a was removed by distillation,
and aldehyde 3a was distilled in a vacuum. Yield 4.6 g
(0.023 mol, 60%), bp 137‒138°C (4 mmHg), nD20
1.5104. IR spectrum, ν, cm–1: 2890, 2848, 1720, 1450,
1417, 1352, 1064, 1028. Mass spectrum, m/z (Irel, %):
192.2 (1) [M]+, 180.2 (19), 163.1 (9), 135.2 (100),
107.1 (18), 93.1 (54), 81.0 (7), 67.0 (5), 55.1 (5), 41.1
(6). Found, %: С 81.32; Н 10.55. С13Н20О. Calculated,
%: С 81.20; Н 10.48. М 192.1.
1
The Н NMR spectra of compounds 5a‒5d contain
proton signals of the 2,4-dinitrophenylhydrazone
fragment. The aromatic proton signals are observed at
7.8‒9.0 ppm. The N‒H proton signal is shifted far
downfield (11.00‒11.35 ppm) due to the strong
electron-acceptor effect of the 2,4-dinitrophenyl
substituent. The adamantyl proton signals appear as
two multiplets at 1.55‒2.0 ppm, and the signals of the
R1 and R2 substituents are observed at 0.85‒1.45 ppm.
The number of protons in R1 and R2 in hydrazones
5a‒5d corresponds to the number of protons in R1 and
2-(Adamantan-1-yl)pentanal (3b) was prepared
similarly from 10 g (0.12 mol) of pentanal 2b and 4 g
(0.03 mol) of propellane 1 at 35‒40°С for 5 h. Yield
5.0 g (0.22 mol, 75.6), bp 141‒143°C (3 mmHg), nD20
1.5150. IR spectrum, ν, cm–1: 2886, 2840, 1715, 1450,
1417, 1350, 1061, 1021. Mass spectrum, m/z (Irel, %):
220.2 (5) [M]+, 192.1 (1), 163.1 (1), 135.2 (100), 107.1
(10), 93.1 (19), 79.1 (20), 67.1 (5), 55.1 (2), 41.1 (7).
Found, %: С 81.90; Н 11.04. С15Н24О. Calculated, %:
С 81.76; Н 10.98. М 220.2.
1
R2 in aldehydes 3a‒3d. Thus, the Н NMR spectra
provide reliable evidence for the structure of both
hydrazones 5a‒5d and aldehydes 3a‒3d. The
1
observation in the Н NMR spectra of hydrazones 5a‒
2-(Adamantan-1-yl)hexanal (3с) was prepared
similarly from 12 g (0.12 mol) of hexanal 2с and 4 g
(0.03 mol) of propellane 1. Yield 5 g (0.023 mol,
78%), bp 151‒154°C (3 mmHg), nD20 1.5216. IR
spectrum, ν, cm–1: 2884, 2842, 1715, 1451, 1412,
1348, 1058, 1020. Mass spectrum, m/z (Irel, %): 234.2
(4) [M]+, 206.1 (2), 163.1 (1), 135.2 (100), 107.1 (9),
93.1 (23), 79.1 (23), 67.1 (5), 55.1 (7), 41.1 (6). Found,
%: С 82.06; Н 11.26. С16Н26О. Calculated, %: С
81.99; Н 11.18. М 234.2.
5d of the СН=N proton signal at 7.60‒8.59 ppm gives
clear evidence showing that propellane 1 has added by
the Сα‒Н bond rather than carbonyl С(О)‒Н bond of
the starting aldehydes.
Thus, the reaction of propellane 1 with aliphatic
aldehydes occurs in mild conditions, involving the
Сα‒Н bond of the aldehyde and forming branched 2-
(adamantan-1-yl)alkanals 3а‒3d in a yield of 60‒78%.
EXPERIMENTAL
2-(Adamantan-1-yl)-2-mehtylpropanal (3d) was
prepared similarly from 13 g (0.18 mol) of 2-methyl-
propanal 2d and 4 g (0.03 mol) of propellane 1. Yield
4.6 g (0.022 mol, 76%), bp 121‒123°C (4 mmHg), nD20
1.5185. IR spectrum, ν, cm–1: 2892, 2846, 1718, 1452,
1420, 1351, 1062, 1026. Mass spectrum, m/z (Irel, %):
206.2 (1) [M]+, 177.2 (5) [M ‒ СНО], 135.2 (100),
107.1 (7), 93.1 (16), 79.1 (14), 67.0 (6), 55.1 (4), 41.1
(5). Found, %: С 81.65; Н 10.92. С14Н22О. Calculated,
%: С 81.50; Н 10.75. М 206.2.
Propellane 1 was prepared by the procedure in [11].
Aliphatic aldehydes and 2,4-dinitrophenylhydrazone
are commercial products. Solvents were dried by
conventional procedures.
The mass spectra were registered on an Agilent GC
5975/MSD 7820 instrument. Gas chromatographic
separation was performed on a 30-m HP-5MS quartz
capillary column, carrier gas helium. The oven
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MOKHOV et al.
644
Hydrazones 5а‒5d. A solution of m mol of
NMR spectrum, δ, ppm: 1.1 s (6H, 2CH3), 1.70‒1.99
m (15H, Ad), 7.9 s (1Н, Ph), 8.1 s (1Н, Ph), 8.8 s (1Н,
Ph), 8.4 s (1H, CH=N), 11.3 s (1H, NH). Mass spec-
trum, m/z (Irel, %): 386 (2.3) [M]+, 135 (100) [Ad]+, 41
(9.4) [С3Н5]+. Found, %: С 62.22; Н 6.86; N 14.57.
C20H26N4O4. Calculated, %: С 62.16; Н 6.78; N 14.50.
М 386.2.
aldehyde in 5 mL of ethanol was added to a stirred
mixture of n mol of dinitrophenylhydrazine 4, 10 mL
of H2SO4, 15 mL of H2O, and 30 mL of ethanol. The
reaction mixture was held for 15 min at 25°С, and the
crystals that formed were filtered off and recrystallized
from isopropanol.
1-[2-(Adamantan-1-yl)propylidene]-2-(2,4-di-
nitrophenyl)hydrazine (5a) was prepared from 2.4 g
(0.012 mol) of dinitrophenylhydrazine 4 and 0.01 mol
of aldehyde 3a. Yield 3.4 g (0.009 mol, 84%), yellow
FUNDING
The work was funded by the Ministry for Education
and Science of the Russian Federation in the
framework of the basic part of the State order for
2017–2019 (project no. 4.7491.2017/BCh) using the
equipment purchased under the Program for Strategic
Development of the Volga State Technical University
for 2012–2016.
1
crystals, mp 80‒81°С. Н NMR spectrum, δ, ppm:
0.95‒0.97 m (3H, CH3), 1.68‒2.0 m (15H, 1-Ad), 2.0‒
2.1 m (1Н, СН), 7.92 s (1Н, Ph), 8.2 s (1Н, Ph), 8.85 s
(1Н, Ph), 8.59 s (1H, CH=N), 11.35 s (1H, NH). Mass
spectrum, m/z (Irel, %): 372 (1) [M]+, 135 (14) [Ad]+,
41 (100) [С3Н5]+. Found, %: С 61.34; Н 6.56; N 15.12.
C19H24N4O4. Calculated, %: С 61.28; Н 6.50; N 15.04.
М 372.2.
CONFLICT OF INTEREST
The authors declare no conflict of interest.
REFERENCES
1-[2-(Adamantan-1-yl)pentylidene]-2-(2,4-di-
nitrophenyl)hydrazine (5b) was prepared similarly
from 2.2 g (0.011 mol) of hydrazine 4 and 2 g (0.009 mol)
of aldehyde 3b. Yield 3.5 g (0.0084 mol, 93%); yellow
1
crystals, mp 178‒180°С (i-PrOH). Н NMR spectrum,
1. Butov, G.M. and Mokhov, V.M., Russ. J. Org.
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δ, ppm: 0.91‒0.94 m (3H, CH3), 1.45‒1.49 m (4Н,
2СН2), 1.59‒1.97 m (15H, Ad), 1.98‒2.0 m (1Н, СН),
7.9 s (1Н, Ph), 8.25 s (1Н, Ph), 9.0 s (1Н, Ph), 7.94 s
(1H, CH=N), 11.12 s (1H, NH). Mass spectrum, m/z
(Irel, %): 400 (2.2) [M]+, 135 (22) [Ad]+, 41 (100)
2. Stepanov, F.N. and Dovgan’, N.L., Zh. Org. Khim.,
1968, vol. 4, p. 277.
3. Polis, Ya.Yu., Raugel’, B.P., and Liepin’sh, E.E., USSR
Inventor’s Certificate no. 1793313, 1977; Byull.
Izobret., 1977, no. 5.
+
[С3Н5]+, 233 (11) [M ‒ C6H3(NO2)2 ]. Found, %: С
63.01; Н 7.12; N 13.80. C21H28N4O4. Calculated, %: С
62.98; Н 7.05; N 13.99. М 400.2.
4. Voloboev, S.N., Butenko, L.N., and Novakov, I.A.,
Russ. J. Gen. Chem., 2001, vol. 71, p. 1121. doi
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1-[2-(Adamantan-1-yl)hexylidene]-2-(2,4-di-
nitrophenyl)hydrazine (5с) was prepared similarly
from 2 g (0.01 mol) of hydrazine 4 and 2 g (0.0085 mol)
of aldehyde 3с. Yield 3.6 g (0.0083 mol, 98%); yellow
5. Bott, K., Angew. Chem., 1968, vol. 80, p. 970. doi
10.1002/ange.19680802211
1
6. Kell, D.R. and McQuill, F.J., J. Chem. Soc., D: Chem.
Commun., 1970, p. 599. doi 10.1039/C29700000599
crystals, mp 167‒168°С (i-PrOH). Н NMR spectrum,
δ, ppm: 0.85‒0.9 m (3H, CH3), 1.39‒1.42 (6Н, 3СН2),
1.55‒1.95 m (15H, Ad), 1.97‒1.99 m (1Н, СН), 7.60 s
(1H, CH=N), 7.80 s (1Н, Ph), 8.24 s (1Н, Ph), 9.0 s
(1Н, Ph), 11.0 s (1H, NH). Mass spectrum, m/z (Irel,
%): 414 (8) [M]+, 135 (100) [Ad]+, 41 (18) [С3Н5]+.
Found, %: С 63.82; Н 7.34; N 13.66. C22H30N4O4.
Calculated, %: С 63.75; Н 7.30; N 13.52. М 414.2.
7. Buckle, M.J.C., Fleming, I., Gil, S., and Pang, K.L.Ch.,
Org. Biomol. Chem., 2004, vol. 2, p. 749. doi 10.1039/
B313446F
8. No, B.I., Butov, G.M., Mokhov, V.M., and Parshin, G.Yu.,
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10.1023/A:1021680519152
1-[2-(Adamantan-1-yl)-2-methylpropylidene]-2-
(2,4-dinitrophenyl)hydrazine (5d) was prepared simi-
larly from 2.3 g (0.011 mol) of hydrazine 4 and 2 g
(0.01 mol) of aldehyde 3d. Yield 3.8 g (0.0094 mol,
10. Mokhov, V.M., Butov, G.M., and Saad, K.R., Russ.
J. Org. Chem., 2014, vol. 50, p. 1276. doi 10.1134/
S1070428014090073
1
96%); yellow crystals, mp 250‒251°С (i-PrOH). Н
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CHEMICAL TRANSFORMATIONS OF TETRACYCLO[3.3.1.1.3,7.0.1,3]DECANE
645
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