Selective hydroxylation of adamantane and its derivatives

Article abstract of DOI:10.1134/S1070428009080041

A general method was developed for hydroxylation into the nodal position of adamantane and its 1- and 2-substituted derivatives employing systems H ₂O-CBr₄ (BrCCl₃, CCl₄) in the presence of complexes of Pd, Ni, Ru, Co, Mo, W, and Fe. The oxidants in the systems are hypochlorous (HOCl) or hypobromous (HOBr) acids generated from water and halomethanes under the reaction conditions.

Full text of DOI:10.1134/S1070428009080041

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 8, pp. 1137−1142. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © R.I. Khusnutdinov, N.A. Shchadneva, L.F. Mukhametshina, U.M. Dzhemilev, 2009, published in Zhurnal Organicheskoi
Khimii, 2009, Vol. 45, No. 8, pp. 1152−1156.
Selective Hydroxylation of Adamantane and Its Derivatives
R. I. Khusnutdinov, N.A. Shchadneva, L. F. Mukhametshina, and U. M. Dzhemilev
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, Ufa, 450075 Russia
e-mail: ink@anrb.ru
Received October 27, 2008
Abstract—A general method was developed for hydroxylation into the nodal position of adamantane and its 1-
and 2-substituted derivatives employing systems H2O–CBr4 (BrCCl3, CCl4) in the presence of complexes of Pd, Ni,
Ru, Co, Mo, W, and Fe. The oxidants in the systems are hypochlorous (HOCl) or hypobromous (HOBr) acids
generated from water and halomethanes under the reaction conditions.
DOI: 10.1134/S1070428009080041
The adamantale series hydrocarbons are more prone
to oxidation than alkanes and ordinary cycloalkanes [1,
2]. Versatile oxidants were applied to the catalytic
oxidation of adamantane and its derivatives: oxygen,
hydrogen peroxide, hydroperoxides, iodosobenzene, 2,6-
dichloropyridine N-oxide [1–4]. The oxidation can be
catalyzed by enzymes (cytochromes, cytochrome P-450),
and by organometallic compounds of Co, Mn, Fe, Ru, Pt
[1–4].Due to the important involvement of radical
processes these methods of adamantane oxidation are
characterized by low selectivity and lead to the formation
of mixtures of 1- and 2-hydroxyadamantanes and 2-ada-
mantanone.
1-adamantanol (IIa) which was obtained in 85% yield.
In this system the oxidation was performed by
hypobromous acid generated from H2O and CBr4 under
the action of Mo(CO)6.
In this study we carried on the search for efficient
catalysts for oxidation of adamantane (I) and its
derivatives using halomethanes (CBr4, CBrCl3, CCl4) and
water.
The adamantane hydroxylation can be performed not
only using the system CBr4–H2O–Mo(CO)6, but also
applying as catalyst complexes of Ru, W, Fe, Ni, Co, and
Pd. In the reaction of adamantane (I) with a mixture
CBr4–H2O, 1 : 80, in the presence of a ruthenium complex
Ru(OH)Cl3 ([AdH] : [Ru] = 100:1) at 140°C within 10 h
1-adamantanol (IIa) selectively formed in 33% yield. On
raising the catalyst concentration to 3 mol% the yield of
alcohol IIa increased to 55%. The adamantane (I)
conversion and the yield of compound IIa depend
decisively on water concentration, with a maximum
efficiency at 40-fold water excess with respect to
adamantane and CBr4. The 8-fold decrease in water
amount (CBr4–H2O, 1 : 10) resulted in diminishing of
adamantane (I) conversion to 32% in spite of raising the
reaction temperature (160°C, 9 h), and 1-bromoada-
mantane became the main reaction product.
In the previous report [5] we demonstrated that
applying the system CBr4–H2O–Mo(CO)6 it was possible
to carry out a selective oxidation of adamantane (I) to
+ BrCCl +
H2O
3
1 : 1 : 40
I
O
PdCl2(PPh3)2
+
OH
160oC, 9 h, 82%
IIa
III
At replacement of CBr4 by BrCCl3 in the composition
of the oxidating system the adamantane (I) conversion
grew to 89% (see the table, run no. 7). Whereas at the use
of catalyst NiCl2(PPh3)2, NiCl2[P(C4H9)3]2,
CoCl2[(Ph2PCH2)2]2 the main reaction product is
1 : 1
R = OH (a), Cl (b), Br (c), COCH3 (d), NH2 (e), CH(NH2)CH3
(f), COOH (g), COCl (h). III, R = O; X, R = Br (a), NH2 (b);
XI, R = O (a), Br (b), NH2 (c).
1137

KHUSNUTDINOV et al.
1138
Effect of the catalyst nature and reaction conditions on adamantane oxidation with a system CHlg4–H2O under the action of
transition metal complexes
Molar ratio
[cat]:[AdH]:[CHlg4]:[H2O]
Yield, %
Run
no.
Catalyst
CHlg4
Temperature, OC Time, h
°
IIa
III
1
Without catalyst
CBr4
0 : 1 : 1 : 1
1 : 100 : 100 : 8000
3 : 100 : 100 : 8000
3 : 100 : 100 : 4000
3 : 100 : 100 : 2000
3 : 100 : 100 : 1000
"
140
10
"
3
2
Ru(OH)Cl3
"
"
"
33
55
62
30
28
89
–
–
–
–
–
–
3
"
"
"
"
"
"
"
4
"
160
"
9
"
5a
6b
7
"
"
"
"
CBrCl3
"
"
8
9
NiCl2(PPh3)2
"
"
"
"
"
"
"
"
"
"
"
"
"
"
"
55
59
66
41
83
78
89
64
70
34
–
–
NiCl2[P(C4H9)3]2
"
10 CoCl2[(Ph2PCH2)2]2
11 PdCl2(PPh3)2
12 Mo(CO)6
"
"
"
–
"
"
"
41
–
"
"
"
13 W(CO)6
"
"
"
–
14 Cr(CO)6
"
"
"
"
–
15 Fe3(CO)12
"
"
–
16 Mo(CO)6
CCl4
"
140
"
13
"
10
66
17 Mo(CO)6–TBAB, 1:1
a Formed also 30% of 1-bromoadamantane (IIc). bFormed also 28% of 1-bromoadamantane (IIc).
1-adamantanol (IIa), in the presence of PdCl2(PPh3)2
alongside compound IIa forms an equimolar quantity of
2-adamantanone (III).
140°C, but the complete conversion of adamantane (I)
required longer heating (13 h). The reaction involving CCl4
occurred with a low selectivity: In the reaction mixture
alongside alcohol IIa were found adamantanone III, 1,3-
adamantanediol (IVa), and 3-chloroadamantan-1-ol (IVb)
in a ratio 4:1:2:1. When the reaction was carried out in
the presence of Mo(CO)6 with the addition of phase-
transfer catalyst tetrabutylammonium bromide (TBAB),
1:1, then the main product was adamantanone III.
Metal carbonyls Mo(CO)6, W(CO)6, Cr(CO)6, and
Fe3(CO)12 turned out to be sufficiently active catalysts
of adamantane (I) hydroxylation in the oxidative system
BrCCl3–H2O, 1:40. The reaction in their presence within
9 h at 160°C afforded 1-adamantanol (IIa) in 83, 78, 89,
and 64% yield respectively.
The progress of adamantane (I) hydroxylation was
monitored by GLC. We determined the optimum con-
centrations of the catalyst and reagents components, the
reaction conditions suitable for preparation of 1-ada-
mantanol (IIa) and adamantanone III (see the table).
Introducing CCl4 into the composition of the oxidative
system made it possible to reduce the temperature to
+ CCl4
+
H2O
In the reaction mixture alongside compounds IIa and
III GLC and GC-MS methods revealed the presence
of bromoform and chloroform showing the involvement
of CBr4, BrCCl3, and CCl4 in the process of adamantane
oxidation. The reaction does not proceed in the absence
of halomethanes. The iodometric titration of the quickly
cooled reaction mixture showed the presence of active
bromine (c8.48 mg ml−1) and active chlorine (c 3.2 mg ml−1)
I
1 : 1 : 40
O
_
Mo(CO)6 TBAB, 1 : 1
+
OH
140°C, 13 h, ~100%
IIa
III
1 : 2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 8 2009

SELECTIVE HYDROXYLATION OF ADAMANTANE AND ITS DERIVATIVES
1139
demonstrating the formation of hypobromous (HOBr) and
hypochlorous (HOCl) acids respectively. The formation
of HOCl was confirmed by the appearance in the UV
spectrum of a characteristic maximum in the region 229–
236 nm. The data obtained suggest that the oxidation of
adamantane and its derivatives is effected by HOBr and
HOCl [5].
The hydroxylation of compounds IIa–IIh in all cases
proceeded chemoselectively at the free nodal carbon
atom. For instance, the oxidation of 1,3-dibromo-
adamantane (VIII) in the system BrCCl3–H2O–
Mo(CO)6 gave rise to 1,3-dibromo-5-adamantanol (IX).
The hydroxylation direction to the nodal position is
conserved also in the series of 2-substituted adamantanes:
2-adamantanone (III), 2-bromo- (Xa), and 2-ada-
mantanamine (Xb).
We succeeded in bringing into the hydroxylation
reaction a homolog of adamantane (I), diamantane V
whose oxidation with a system CBrCl3–H2O in the
presence of Mo(CO)6 also occurred at the nodal carbon
atoms giving a mixture of 1- and 4-diadamantanols (VI,
VII) in a ratio 2:1 and an overall yield 75% (Scheme 1).
4-Aminoadamantan-1-ol (XIc) formed as a mixture
of two stereoisomers (syn/anti 1.6:1), distinguished by
the relative positions of amino and hydroxy groups. The
fact of the formation of mixture of syn- and anti-isomers
XIc and their ratio were established by 13C NMR spec-
troscopy
As showed the study of a series of substituted ada-
mantanes, the oxidation system H2O–BrCCl3–Mo(CO)6
([cat] : [AdH] : [BrCCl3] : [H2O] = 1 : 100 : 100 : 4000)
provided the hydroxylation of the following substrates:
adamantanol (IIa), 1-chloro- (IIb), 1-bromo- (IIc),1-acetyl-
(IId), 1-amino- (IIe), 1-(1-aminoethyl)- (IIf)–
adamantanes, 1-adamantanecarboxylic acid (IIg), and
1-adamantanecarbonyl chloride (IIh) (Scheme 2).
Scheme 3.
Br
+
BrCCl3 +
H2O
Br
Br
VIII
Mo(CO)6
Scheme 1.
HO
Br
150°C, 10 h, ~100%
+ CBrCl +
H2O
3
IX
V
R
OH
Mo(CO)6
150°C, 10 h, 80_88%
+
+
H2O
BrCCl3
Mo(CO)6
+
140°C, 12 h, 75%
OH
HO
XIa_XIc
III, Xa, Xb
1 : 2
VI
VII
III, R = O; X, R = Br (a), NH2 (b); XI, R = O (a), Br (b),
NH2 (c).
Scheme 2.
R
Scheme 4.
CH3
+ BrCCl +
H2O
3
+
+
H2O
BrCCl3
IIa_IIh
R
CH3
XII
Mo(CO)6
150°C, 6 h, 58_99%
CH3
OH
Mo(CO)6
IVa_IVh
HO
CH3
160°C, 6 h, 68%
R = OH (a), Cl(b), Br (c), COCH3 (d), NH2 (e), CH(NH2)CH3
(f), COOH (g), COCl (h).
XIII
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KHUSNUTDINOV et al.
1140
In the hydroxylation of adamantanes containing polar
stirred at 140–180°C for 3–12 h. On completion of the
reaction the reactor or ampoule was cooled to room
temperature, opened, the product was extracted into
dichloromethane (3×5 ml), the solvent was distilled off,
and the residue was either distilled in a vacuum or
crystallized from hexane or ethanol. The yields are given
calculated on the consumed adamantane (GLC analysis,
internal reference). The structure of compounds was
confirmed by comparison with authentic samples and
handbook references.
substituents a high activity was provided both by the
carbonyl complexes of Mo, W, Fe and by phosphine
complexes of Ni, Co, Pd, and Rh. The oxidation time
essentially depended on the reaction temperature. Raising
the temperature from 140 to 180°C accelerated the reac-
tion more than 4-fold (3 h at 180°C, 5 h at 170°C, 10 h at
150°C, 13 h at 140°C). Prolonged reaction at high
temperature (170–180°C) is unwanted for it results in
the formation of chlorinated (brominated) products.
The hydroxylation of 1,3-dimethyladamantane (XII)
occurred at the free nodal carbon atom; no oxidation
products of the methyl group were detected (Scheme 4).
1-Adamantanol (IIa). Yield 89%, mp 282–283°C
(subl.) {283–284°C (subl.) [6]}. 13C NMR spectrum, δ,
ppm: 30.85 (C3,5,7), 36.15 (C4,6,10), 45.32 (C2,8,9), 67.90
(C1). Mass spectrum, m/z (Irel, %): 152 [M]+ (24), 109
(5), 96 (7), 95 (100), 94 (14), 79 (5), 77 (7), 67 (5), 55 (5),
43 (15), 41 (12), 39 (10), 29 (7). Found, %: C 78.87;
H 10.57. C10H16O. Calculated, %: C 78.89; H 10.59.
As follows from the data obtained, the best catalysts
for hydroxylation of adamantane and its derivatives by
the reagent CBr4 (BrCCl3, or CCl4)–H2O besides
Mo(CO)6 are ruthenium and chromium complexes. At
employing as catalyst PdCl2(PPh3)2 a deeper oxidation
of adamantine occurred giving 2-adamantanone in 41%
yield.
2-Adamantanone (III). Yield 66%, mp 256–257°C
(subl.) {256–258°C [7]}. 13C NMR spectrum, δ, ppm:
27.64 (C5,7), 36.31 (C6), 39.20 (C4,8,9,10), 46.92 (C1,3),
216.59 (C2). Found, %: C 79.78; H 9.12. C10H14O.
Calculated, %: C 79.95; H 9.39.
EXPERIMENTAL
1,3-Adamantanediol (IVa). Yield 86%, mp 308–
309°C (subl.) {310°C [8]}. 13C NMR spectrum, δ, ppm:
31.17 (C5,7), 43.45 (C4,8,9,10), 51.94 (C2), 69.52 (C1,3).
Found, %: C 71.08; H 9.42. C10H16O2. Calculated, %:
C 71.39; H 9.58.
The purity of compounds obtained was checked and
the composition of reaction products was determined by
GLC on a chromatograph Chrom-5, column 1.2 m ×
3 mm, stationary phase 5% SE-30 on Chromaton N-AW-
HMDS, ramp from 50 to 280°C at a rate 8 deg/min,
carrier gas helium.
3-Chloroadamantan-1-ol (IVb). Yield 80%, mp
205°C (subl.) {205.5°C [9]}. 13C NMR spectrum, δ, ppm:
26.95 (C5,7), 36.94 (C6), 44.77 (C8,9), 47.90 (C4,10), 54.05
(C2), 69.24 (C3), 72.94 (C1). Found, %: C 64.21; H 7.89;
Cl 18.82. C10H15ClO. Calculated, %: C 64.33; H 8.39;
Cl 18.99.
IR spectra were recorded on a spectrophotometer
Specord 75IR (from films or mulls in mineral oil) in the
range 550–3600 cm–1. 13C NMR spectra were registered
on a spectrometer JEOL FX 90Q with operating
frequency 90 ΜHz in CDCl3, chemical shifts were
measured with respect to TMS. Mass spectra were
measured on a GC-MS instrument Finnigan MAT-112S
in the electron impact mode at ionizing energy 70 eV and
the temperature of ion source 22°C. Elemental
composition of compounds was determined on an analyzer
Karlo Erba, model 1106.
3-Bromoadamantan-1-ol (IVc). Yield 92%, mp
158–159°C (hexane) {159–160°C (petroleum ether)
[10]}. 13C NMR spectrum, δ, ppm: 73.54 (C1), 54.48
(C2), 68.59 (C3), 48.37 (C4,10), 26.19 (C5,7), 37.26 (C6),
44.13 (C8,9). Mass spectrum, m/z (Irel, %): 166 [M]+
(lacking), 230 (5), 152 (31), 151 (94), 133 (7), 109 (7),
107 (10), 96 (26), 95 (100), 94 (14), 93 (17), 92 (7), 91
(17), 81 (8), 79 (7), 77 (16), 67 (16), 67 (13), 65 (7), 55
(14), 42 (12), 41 (19), 39 (20), 29 (48). Found, %: C 51.77;
H 6.48; Br 34.52. C10H15BrO. Calculated, %: C 51.96;
H 6.54; Br 34.57.
Hydroxylation of adamantane and its derivatives.
Into a pressure microreactor of stainless steel (V 17 ml)
or in a glass ampoule (V 20 ml) (the results of parallel
runs were practically identical) was charged under argon
0.1–0.3 mmol of catalyst, 10 mmol of adamantane (or its
derivative), 10 mmol of CBr4 (BrCCl3 or CCl4), and 400–
800 mmol of water. The reactor was hermetically closed
(the ampoule was sealed), and the reaction mixture was
1-(3-Hydroxy-1-adamantyl)ethanone (IVd). Yield
98%, mp 86–87°C (hexane) {89–91°C (ethyl acetate–
hexane) [11]}. IR spectrum, ν, cm–1: 3395 (OH), 1680
(C=O). 13C NMR spectrum, δ, ppm: 67.92 (C1), 45.64
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 8 2009

SELECTIVE HYDROXYLATION OF ADAMANTANE AND ITS DERIVATIVES
1141
(C2), 49.70 (C3), 37.02 (C4,10), 30.13 (C5,7), 35.21 (C6),
44.19 (C8,9), 212.58 (C=O), 24.39 (CH3). Mass
spectrum, m/z (Irel, %): 194 [M]+ (7), 152 (9), 151 (100),
133 (7), 109 (7), 107 (19), 95 (36), 93 (48), 91 (7), 81
(11), 79 (8), 77 (9), 67 (11), 65 (7), 59 (9), 55 (9), 43 (38),
41 (12), 39 (9), 29 (7). Found, %: C 74.05; H 9.29.
C12H18O2. Calculated, %: C 74.19; H 9.34.
Br 49.98. C10H14Br2O. Calculated, %: C 38.74; H 4.55;
Br 51.55.
1-Hydroxyadamantan-4-one (XIa). Yield 85%, mp
320–321°C (subl.) {319–322°C (CCl4) [13]}. 13C NMR
spectrum, δ, ppm: 29.95 (C7), 38.95 (C8,10), 45.18 (C2,6,9),
46.85 (C3,5), 67.78 (C1), 216.21 (C4). Mass spectrum,
m/z (Irel, %): 166 [M]+ (25), 148 (6), 109 (6), 108 (10),
107 (5), 97 (10), 96 (20), 95 (100), 94 (10), 80 (7), 79 (8),
77 (6), 67 (5), 55 (10), 53 (11), 43 (12), 41 (24), 39 (23).
Found, %: C 77.48; H 8.46. C10H16O2. Calculated, %:
C 72.25; H 8.49.
3-Aminoadamantan-1-ol (IVe). Yield 80%, mp 264–
265°C (267°C [9]). 13C NMR spectrum, δ, ppm: 68.25
(C1), 45.71 (C2), 47.18 (C3), 46.10 (C4,10), 30.38 (C5,7),
36.81 (C6), 45.39 (C8,9). Found, %: C 71.43; H 10.07;
N 8.42. C10H17NO. Calculated, %: C 71.81; H 10.25;
N 8.37.
4-Bromoadamantan-1-ol (XIb). Yield 80%, t.subl.
89°C (2 mm Hg). 13C NMR spectrum, δ, ppm: 32.58
(C1,3), 33.49 (C7), 36.51 (C8,10), 41.87 (C4,9), 44.50 (C6),
62.25 (C2), 72.09 (C5). Found, %: C 51.82; H 6.45;
Br 34.49. C10H15BrO. Calculated, %: C 51.96; H 6.96;
Br 34.57.
3-(1-Aminoethyl)adamantan-1-ol (IVf). Yield 99%,
mp 111–112°C (ethanol). 13C NMR spectrum, δ, ppm:
16.56 (CH3), 28.32 (C5,7), 35.61 (C4,10), 36.69 (C6), 36.88
(C2), 44.80 (C8,9), 45.74 (C1), 55.54 (CHNH2), 66.42 (C3).
Found, %: C 73.79; H 10.84; N 7.17. C12H21NO.
Calculated, %: C 73.48; H 10.71; N 6.95.
4-Aminoadamantan-1-ol (XIc). Yield 88%, mp 256–
260°C (ethanol) {258–260°C (toluene) [14]}. 13C NMR
spectrum, δ, ppm, syn-isomer: 29.73 (C7), 36.29 (C6,10),
37.68 (C3,5), 38.80 (C2,9), 45.64 (C8), 54.07 (C4), 67.52
(C1); anti-isomer: 67.45 (C1), 44.88 (C2,9), 36.92 (C3,5),
54.55 (C4), 29.50 (C6,10), 30.07 (C7), 45.83 (C8). Found,
%: C 71.48; H 19.97; N 8.48. C10H17NO. Calculated, %:
C 71.81; H 10.25; N 8.37.
3-Hydroxy-1-adamantanecarboxylic acid (IVg).
Yield 58%, t.subl. 120°C (2 mm Hg). 13C NMR spectrum,
δ, ppm: 28.53 (C5,7), 36.03 (C6), 38.29 (C4,10), 42.91 (C3),
44.51 (C8,9), 48.23 (C2), 68.74 (C1), 183.13 (COOH).
Found, %: C 67.19; H 8.15. C11H16NO3. Calculated, %:
C 67.32; H 8.21.
3,5-Dimethyladamantan-1-ol (XIII). Yield 68%, mp
95–96°C (ethanol) {95.2–96.2°C [15]}. 13C NMR
spectrum, δ, ppm: 23.58 (C7), 30.37 (CH3), 33.49 (C3,5),
43.23 (C6,10), 45.72 (C8), 50.59 (C4), 54.47 (C2,9), 72.96
(C1). Found, %: C 79.85; H 11.05. C12H20O. Calculated,
%: C 79.94; H 11.18.
3-Hydroxy-1-adamantanecarbonyl chloride
(IVh). Yield 91%, t.subl. 111–112°C (1 mm Hg). 13C
NMR spectrum, δ, ppm: 27.37 (C5,7), 37.26 (C6), 41.18
(C4,10), 45.76 (C8,9), 48.53 (C2), 53.55 (C3), 67.76 (C1),
178.32 (COCl). Found, %: C 61.32; H 6.89; Cl 16.48.
C11H15ClO2. Calculated, %: C 51.53; H 7.04; Cl 16.51.
The study was carried out under a financial support
of the Russian Foundation for Basic Research (grant
no. 08-03-97005), of the program of the President of RF
for support of leading scientific schools (grant NSh
7470.2006.3), and of the program of the Division of
Chemistry and Material Science of the RussianAcademy
of Sciences no. 8.
Diamantan-1-ol (VI) [12]. Yield 50%. 13C NMR
spectrum, δ, ppm: 25.33 (C4), 30.56 (C9), 32.60 (C3,14),
36.81 (C6), 37.68 (C8,10), 38.05 (C5), 40.02 (C7,11), 43.44
(C2,12), 46.40 (C13), 70.82 (C1). Mass spectrum, m/z (Irel,
%): 204 [M]+ (51), 186 (100), 130 (36), 129 (26), 95 (85),
94 (87), 92 (22), 91 (24), 79 (20). Found, %: C 82.21;
H 9.83. C14H20O. Calculated, %: C 82.30; H 9.86.
Diamantan-4-ol (VII) [12]. Yield 25%. 13C NMR
spectrum, δ, ppm: 25.36 (C9), 35.92 (C1,7,11), 36.81, 37.15
(C8,10,13), 41.90 (C2,6,12), 45.83 (C3,5,14), 67.87 (C4). Mass
spectrum, m/z (Irel, %): 204 [M]+ (100), 183 (3), 109 (20),
108 (14), 107 (18), 96 (15). Found, %: C 82.15; H 9.78.
C14H20O. Calculated, %: C 82.30; H 9.86.
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p. 483.
3,5-Dibromoadamantan-1-ol (IX). Yield ~100%,
t.subl. 98°C (1 mm Hg). 13C NMR spectrum, δ, ppm:
29.98 (C7), 45.25 (C6), 49.20 (C8,10), 53.70 (C4,9), 55.90
(C2), 65.08 (C1,3), 72.97 (C5). Found, %: C 38.63; H 4.41;
3. Landa, S., Burkkhard, I., and Vais, I., Sb. VSCHT Prazc D,
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KHUSNUTDINOV et al.
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