Synthesis of heteroaromatic N-β-glycosides of N-acetylglucosamine under the conditions of phase transfer catalysis: I. Glucosaminides of 2-oxobenzazoles

Article abstract of DOI:10.1134/S1068162006060082

Glycosylation of benzothiazolone-2, 5-methylbenzoxazolone-2, and benzothiazolone-2 with the full acetate of α-D-glucosaminyl chloride in the phase transfer systems investigated (solid-organic solvent and aqueous alkali-organic solvent) regioselectively leads to the corresponding N-β-D-glucosaminides, which is proved by ¹H NMR spectroscopy and X-ray analysis.

Full text of DOI:10.1134/S1068162006060082

ISSN 1068-1620, Russian Journal of Bioorganic Chemistry, 2006, Vol. 32, No. 6, pp. 552–557. © Pleiades Publishing, Inc., 2006.
Original Russian Text © V.O. Kur’yanov, T.A. Chupakhina, A.E. Zemlyakov, V.Ya. Chirva, O.V. Shishkin, S.V. Shishkina, S.A. Kotlyar, G.L. Kamalov, 2006, published in Bioorgan-
icheskaya Khimiya, 2006, Vol. 32, No. 6, pp. 615–620.
Synthesis of Heteroaromatic N-b-Glycosides
of N-Acetylglucosamine under the Conditions of Phase Transfer
Catalysis: I. Glucosaminides of 2-Oxobenzazoles
a 1
a
a
a
b
V. O. Kur’yanov , T. A. Chupakhina , A. E. Zemlyakov , V. Ya. Chirva , O. V. Shishkin ,
b
c
c
S. V. Shishkina , S. A. Kotlyar , and G. L. Kamalov
a
Vernadsky Tauric National University, pr. Vernadskogo 4, Simferopol, Autonomous Republic of Crimea, 95007 Ukraine
b
Institute of Scintillation Materials, Scientific and Technological Complex Institute of Monocrystals,
National Academy of Sciences of Ukraine, Kharkov, Ukraine
c
Bogatsky Physicochemical Institute, National Academy of Sciences of Ukraine, Chernomorskaya doroga 86, Odessa,
270080 Ukraine
Received December 26, 2005; in final form, January 20, 2006
Abstract—Glycosylation of benzothiazolone-2, 5-methylbenzoxazolone-2, and benzothiazolone-2 with the
full acetate of α-D-glucosaminyl chloride in the phase transfer systems investigated (solid–organic solvent and
aqueous alkali–organic solvent) regioselectively leads to the corresponding N-β-D-glucosaminides, which is
1
proved by H NMR spectroscopy and X-ray analysis.
DOI: 10.1134/S1068162006060082
Key words: amide–imide tautomers, crown ethers, N-β-glycosylation, phase transfer catalysis, quaternary
ammonium salts, regioselectivity, X-ray analysis
INTRODUCTION
4-chloro- and 4-phenyl-(2H)-phthalazinone-1 silver
salts with acetobromoglucose leads to the correspond-
ing é-β-glucosides, while (2H)-phthalazinone-1 does
not enter the reaction discussed. In the case of similar
sodium (potassium) derivatives, only 4-phenyl-(2H)-
phthalazinone-1 reacts in aqueous acetone is possible
to give N-β-glucoside; however, é-β-glucoside is not
formed at all [4, 5].
We have established [1] that, under phase transfer
conditions (solid–organic solvent), thiol–thione pairs
of mercapto derivatives of 1,3,4-oxadiazole and 1,2,4-
triazole are easily glucosaminated in the presence of
crown ethers with 2-acetamido-3,4,6-tri-O-acetyl-2-
deoxy-α-D-glucopyranosyl chloride (I) to form a mix-
2
ture of the corresponding S- and N-β-glucosaminides.
We continued the search for new effective and selec-
tive phase transfer glycosylation reactions [1, 2, 6–8] of
heterocyclic compounds and tried the glucosaminyla-
tion with α-chloride (I) of some amide–imidol tau-
tomers [3] [namely, benzoxazolone-2 (II), 5-methyl-
benzoxazolone-2 (III), and benzothiazolone-2 (IV)]
(scheme) in various phase transfer systems (25°ë) in
the presence of CE catalysts and TEBAC.
At the same time, 5-sulfonylbenzoxazol–2-thiol, ben-
zothiazole-2-thiol, and 3-ethylquinazoline-2-thiol regi-
oselectively form only S-β-glucosaminides under simi-
lar conditions [2].
There is no literature information on the selectivity
of PTC glycosylation of heterocyclic compounds with
N-acetylglucosamine derivatives that can undergo lac-
tim–lactam (amide–imidol) tautomeric transformations
[3]. It is only known that some glycosyl donors (neutral
carbohydrates) selectively glycosylate derivatives of
(2ç) phthalazinone-1 at nitrogen or oxygen atoms and
the selectivity of process depends on its conditions and
the nature of the substituent in position 4 of phthalazine
cycle [4, 5]. For example, the glycosylation of
RESULTS AND DISCUSSION
The stoichiometric glucosamination of azoles (II)–
(IV) according our methodA [1, 2, 7, 8] was carried out
in dry acetonitrile in the presence of anhydrous potas-
sium carbonate and catalytic amounts of 15C5, B18C6,
or DB18C6. A mixture of excess glycosyl acceptor was
stirred with α-chloride (I) when the reaction was car-
ried out in biphasic system aqueous alkali–chloroform
(method B according to [9]); potassium hydroxide
1
Corresponding author; phone: (0652) 23-3885;
fax: (0652) 23-2310; e-mail: vladimir@tnu.crimea.ua.
Abbreviations: CE, crown ether; 15C5, 15-crown-5; 18C6, 18-
crown-6; DB18C6, dibenzo-18-crown-6; PTC, phase transfer
catalysis; and TEBAC, triethylbenzylammonium chloride.
2
552

SYNTHESIS OF HETEROAROMATIC N-β-GLYCOSIDES
553
OAc
O
AcO
AcO
AcHN
OAc
OAc
X
O
H
N
Cl
R
R
N
X
O
O
(I)
AcO
AcO
AcO
AcO
+
N
O
HO
X
NHAc
(V)–(VII)
N
R
O
(II)–(IV)
(VIII)
(II), (V) R = H, X = O (III), (VI) R = Me, X = O (IV), (VII) R = H, X = S
Scheme of synthesis of 2-oxobenzazole N-β-glucosaminides (V)–(VII).
served as a base and OEBAC or 15C5, as a phase trans- reactions and the yields of target products are listed in
fer catalyst. The method C consisted in the glycosyla- Table 1.
tion of the azoles in the presence of sodium hydride
We found that, under the conditions described above,
suspension in mineral oil, the process being carried out
the glycosylation reactions by the methods A–C regiose-
as in method A (see the Experimental section).
lectively proceed and exclusively lead to N-β-gly-
The composition of reaction mixture was monitored cosaminides of 2-oxobenzazoles (V)–(VII). Significant
by TLC, while determining the time of full conversion amounts of 2-methyl-(3,4,6-tri-O-acetyl-1,2-dideoxy-α-
of glycosyl donor (I). The products (V)–(VII) were iso- D-glucopyrano)-[1,2-d]-2-oxozoline (VIII), a known [1,
lated in pure state by column chromatography and 7] side product, are also formed. We identified (VIII) with
investigated with the help of 1H NMR spectroscopy and the help of independent sample by TLC only in the reac-
X-ray analysis. The conditions of the phase transfer tion mixtures, because it is unstable and decomposes
Table 1. The conditions of obtaining N-β-glucosaminides (V)–(VII)*
Glycoside Base/method Azole–α-chloride (I)–base molar ratio Catalyst, mol % Reaction time, h
Yield, %
(V)
(V)
(V)
(V)
(V)
(V)
K2CO3
1 : 1 : 1
–
10
6.5
31
38
61
48
43
64
46
43
55
28
33
58
62
57
45
46
52
62
K2CO3
1 : 1 : 4.5
1 : 1 : 1
–
K2CO3/A
K2CO3/A
K2CO3/A
K2CO3/A
15C5, 20
B18C6, 20
DB18C6, 20
15C5, 20
TEBAC, 80
15C5, 80
15C5, 20
–
4.5
9
1 : 1 : 1
1 : 1 : 1
9
1 : 1 : 4.5
2 : 1 : 1.85
2 : 1 : 1.85
1 : 1 : 1.1
1 : 1 : 1
4
(V)** KOH/B
(V)** KOH/B
(V)
(VI)
(VI)
(VI)
(VI)
(VI)
(VI)** KOH/B
(VI)** KOH/B
(VII)
(VII)
5.5
7
NaH/C
7.5
K2CO3
11
K2CO3
1 : 1 : 4.5
1 : 1 : 1
–
7.5
4.5
4
K2CO3/A
K2CO3/A
NaH/C
15C5, 20
15C5, 20
15C5, 20
TEBAC, 80
15C5, 80
15C5, 20
15C5, 20
1 : 1 : 4.5
1 : 1 : 1.1
2 : 1 : 1.85
2 : 1 : 1.85
1 : 1
7
5
7
K2CO3/A
K2CO3/A
3
1 : 4.5
2
* Unless otherwise stated, solvent is acetonitrile; the reaction time corresponds to the full conversion of chloride (I) (TLC monitoring).
** Solvent is CHCl .
3
RUSSIAN JOURNAL OF BIOORGANIC CHEMISTRY Vol. 32 No. 6 2006

554
KUR’YANOV et al.
Table 2. Proton chemical shifts in 1H NMR spectra of com-
pounds (V)–(VII)
results (in comparison with method A) in a decrease in
yields of (V) and (VI) by 20%. The substitution of
15C5 for OEBAC does not affect the yields of target
products (V) and (VI); however, the conversion time of
α-chloride (I) increases, which agrees with the known
ideas o about the catalytic properties of quaternary
ammonium salts and CEs in such phase transfer sys-
tems [10–13].
Glycosides (V) and (VI) were obtained by method
C in the yields similar to those achieved by method A;
however, the reaction times were much longer
(Table 1).
Group or atom
(V)
(VI)
(VII)
H1 (J1,2
)
)
5.66 d (9.3) 5.65 d (9.9) 5.87 d (9.9)
H2 (J2,3
4.58 ddd
(9.6)
4.55 ddd
(9.6)
4.69 ddd
(9.5)
H3 (J3,4
H4 (J4,5
H5, H6
NHAc
OAc
)
5.37 dd (9.9) 5.37 dd (9.8) 5.35 dd (9.3)
5.28 dd (9.5) 5.23 dd (8.7) 5.26 dd (9.0)
)
4.18 m
1.63 s
4.16 m
1.64 s
4.18 m
1.63 s
The structures of compounds synthesized were
1.94 s, 2.02 s 1.94 s, 2.02 s 1.92 s, 2.02 s
2.03 s 2.04 s 2.04 s
1
proved by the methods of H NMR spectroscopy and
X-ray analysis. The chemical shifts and spin–spin cou-
NH (JNH,2
)
8.09 d (9.3) 8.07 d (9.0) 8.05 d (9.0)
1
pling constants of anomeric protons in the H NMR
Alk
–
2.38 s
6.97 d, 7.21 d 7.21 t, 7.37 t
7.62 d, 7.73 d
–
spectra of the isolated individual compounds (V)–(VII)
(δ 5.65–5.87 ppm, J1,2 9.3–9.9 Hz), as well as of other
skeletal protons (Table 2) close to those we earlier
described for N-glycosides [1] allow the presumption
that these are N-β-D-glucosaminides rather than the
corresponding é-glycosides. Nevertheless, this con-
clusion undoubtedly needs an unequivocal proof.
CHarom
7.20 m,
7.35 d, 7.59 d 7.41 s
under the conditions of column chromatography. No cor-
responding products of é-alkylation were found.
It was established (Table 1) that the use of 15C5 in
the reaction by method A provides a minimum time of
reaction (2–4.5 h) and the best yields (52–64%) of
N-glycosides (V)–(VII). Under the experimentally
found optimum conditions at stoichiometric ratio of
reagents, the conversion time of the substrate and yields
of products (V)–(VII) are insignificantly changed even
at increased (by 4.5 times) amount of potassium car-
bonate. The substitution of B18C6 or DB18C6 for
15C5 twofold reduces the glycosylation speed and by
20% the yield of glycoside (V) (Table 1). In the absence
of CE, the yields of target products appreciably
decrease and the reaction times increase.
To this end, we carried out an X-ray study of (V)
(the figure and Tables 3–5), which, as expected, turned
out to be an N-β-D-glucosaminide.
The coordinates of atoms, bond lengths, and torsion
angles in full acetate (V) are given in Tables 3–5. In a
crystal of compound (V), the six-membered pyranose
cycle is in conformation 4ë1 (chair, the folding param-
eters: S = 1.14, Θ = 4.9°, Ψ = 9.7° [14]). All the substit-
uents in the cycle are in equatorial conformation. Note
the difference in lengths of bonds ësp3–O in the carbo-
hydrate residue (O1–C5 1.431 (6) Å and O1–C1
1.399 (5) Å), which is a consequence of the anomeric
effect; this is described for related compounds (cf., e.g.,
[15, 16]).
Thus, we established that the glucosaminylation of
azoles (II)–(IV) under the conditions of the investi-
gated phase transfer processes, the most effective and
convenient of which is methodA, regioselectively leads
to the corresponding N-β-glycosides. We have com-
pared for the first time the data of X-ray analysis and
1H NMR spectroscopy of glycosylation reaction by the
example of (V) and found that, in our opinion, NMR
allows the use of chemical shifts and spin coupling con-
stants of protons to reveal and unequivocally identify
the products of N-β-glycosylation of such type.
The use of excess azole, aqueous potassium hydrox-
ide and almost stoichiometric quantities of OEBAC
(80 mol. % relative to α-chloride) (method B, Table 1)
C21
C8
C9
C20
O3 C7
O10
O9
O1
C6
C1
O2
C10
C19
C12
C11
N2
C5
O4
C13
C2
N1
O8
C17
C3
C4
EXPERIMENTAL
C14
O7
O5
Melting points were determined on a PTP-1 device,
and optical rotation at 20–22°ë, on a Polamat-A pola-
rimeter at λ 546 nm. 1H NMR spectra were obtained on
a Varian VXR-300 (300 MHz) instrument for solutions
in DMSO-d6 with tetramethylsilane as internal stan-
dard. TLC was carried out on precoated plates Sorbfil-
AFB-UV (Sorbpolymer, Russia). Substance spots were
C18
C15
C16
O6
Molecular structure of N-β-glucosaminide (V)
RUSSIAN JOURNAL OF BIOORGANIC CHEMISTRY Vol. 32 No. 6 2006

SYNTHESIS OF HETEROAROMATIC N-β-GLYCOSIDES
555
Table 3. Coordinates (×104, Å) and (in parentheses) equiv-
alent isotropic thermal parameters (×103, Å2 of atoms in a
crystal of (V)
detected by spraying the plates with 2% sulfuric acid
solution in n-butanol followed by heating at 200–
300°C. We used 10 : 1 benzene–ethanol solvent system.
Kieselgel 60 (0.063–0.200 mm, Merck) was used for
the separation of substances by column chromatogra-
phy. The results of elemental analysis of the com-
pounds synthesized corresponded to the calculated val-
ues.
Benzoxazol-2-one, 5-methylbenzoxazol-2-one, and
benzothiazol-2-one were obtained by the procedure
[18]. The reference compound (VIII) was synthesized
by the Lemieux method [19]. TEBAC (99%) was from
Aldrich; crown ethers 15C5 (98%), B18C6 (98%), and
DB18C6 (98%) were from the Bogatsky Physicochem-
ical Institute of the National Academy of Sciences of
Ukraine).
Atom
x
y
z
U(eq)
N1
3215 (7) 11942 (3)
6110 (6) 11927 (3)
5645 (5) 10281 (2)
9243 (6) 11402 (3)
8943 (6) 12892 (3)
6032 (6) 12928 (3)
3529 (5) 10117 (2)
–9 (7) 10299 (3)
1754 (2)
851 (2)
26 (1)
19 (1)
25 (1)
44 (1)
37 (1)
38 (1)
26 (1)
52 (1)
29 (1)
58 (1)
34 (1)
42 (1)
22 (1)
22 (1)
25 (1)
22 (1)
27 (1)
30 (1)
27 (1)
43 (2)
43 (2)
42 (2)
27 (1)
22 (1)
33 (1)
52 (2)
33 (1)
40 (2)
39 (2)
56 (2)
31 (1)
29 (1)
53 (2)
N2
O1
812 (1)
O2
1243 (2)
868 (2)
O3
O4
1909 (1)
2315 (1)
2398 (2)
1663 (1)
1804 (2)
124 (1)
O5
O6
O7
3121 (6)
5991 (9)
5405 (7)
5657 (7)
8494 (2)
7560 (3)
8744 (2)
7144 (3)
O8
Acetonitrile was boiled with P O , fractioned,
2
5
O9
boiled over freshly calcined potash, distilled, and the
distillate was fractioned using a Vigreaux column. Dry
K2CO3 was obtained by its heating for 5 h at 340–
360°ë.
O10
C1
–10 (2)
4746 (8) 11137 (3)
4447 (9) 11118 (3)
3364 (9) 10186 (4)
1003 (2)
1591 (2)
1765 (2)
1524 (2)
939 (2)
C2
X-Ray analysis. Crystals of (V) are rhombic,
ë21ç24N2O10, at –109°ë a = 6.305(1), b = 13.778(4), c =
25.804(5) Å, V = 2241.7(9) Å3, Mr = 464.42, Z = 4, spa-
C3
C4
4419 (9)
4472 (9)
9306 (3)
9425 (3)
3
tial group P212121; dcalc = 1.376 g/cm ; µ(MoKα) =
C5
0.111 mm–1; F (000) = 976. Parameters of elementary
cell and intensity of 2294 independent reflections were
measured on an automatic four-circle Siemens P3/PC
X-ray diffractometer (MoKα, graphite monochromator,
θ/2θ scanning, 2θmax = 50°). The structure was com-
puted by a direct method on a SHELXTL set of pro-
grams [17]. Positions of hydrogen atoms were revealed
from differential synthesis of electronic density and
refined using a rider model with Uiso = nUequiv of no
hydrogen atom connected with the given hydrogen (n =
1.5 for methyl groups and n = 1.2 for other hydrogen
atoms). The structure was refined according to squares
of structural amplitudes, by a full matrix method of the
least squares in anisotropic approximation for nonhy-
drogen atoms (up to wR2 = 0.108) using 2219 reflec-
tions (R1 = 0.046 from 1295 reflections with F > 4σ(F),
S = 0.931). Final coordinates of atoms are given in
Table 3, lengths of bonds, in Table 4, and valent angles,
in Table 5.
C6
8169 (8) 12000 (4)
7337 (9) 13370 (4)
7372 (12) 14293 (4)
5540 (11) 14621 (4)
3729 (11) 14074 (4)
3674 (9) 13128 (4)
5537 (8) 12792 (3)
4120 (10) 12806 (4)
2592 (11) 13595 (4)
1691 (10) 10207 (4)
2142 (11) 10168 (4)
4092 (13) 7660 (4)
2537 (13) 6963 (4)
5543 (10) 8596 (3)
1019 (2)
628 (2)
C7
C8
419 (2)
C9
207 (2)
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
194 (2)
405 (2)
615 (2)
1891 (2)
2000 (3)
2594 (2)
3160 (2)
1823 (2)
2035 (2)
670 (2)
5454 (8)
7942 (4)
–179 (2)
–733 (2)
5292 (13) 8200 (4)
Method A. The corresponding azole (II)–(IV)
(1.37 mmol), finely ground anhydrous ä2ëé3 (0.85 g,
6.17 mmol), and 15C5 (0.054 ml, 0.274 mmol) were
added to a solution of chloride (I) [20] (0.5 g,
1.37 mmol) in dry acetonitrile (30 ml); and the mixture
was stirred at room temperature until the full conver-
sion of chloride (I) (TLC). Solids were filtered off; the
filtrate was evaporated to dryness at a reduced pressure;
and the products (V)–(VII) were isolated by a column
chromatography.
perature until the full conversion of chloride (I) (TLC).
The organic layer was separated; washed with 1 N
KOH (5 ml) and water (2 × 10 ml); dried with anhy-
drous Na2SO4; filtered; and evaporated at a reduced
pressure. Products (V) and (VI) were isolated by a col-
umn chromatography.
Method C. Sodium hydride (0.06 g, 1.64 mmol of
Method B. A mixture of chloride (I) (1.25 g, 60% suspension in mineral oil) was added to a solution
3.42 mmol), azole (II) or (III) (6.84 mmol), TEBAC of azole (II) or (III) (1.37 mmol) in dry acetonitrile
(0.62 g, 2.73 mmol), chloroform (12.5 ml), and 1.25 N (30 ml). The mixture was stirred for 1 h at room tem-
KOH (5 ml, water solution) were stirred at room tem- perature, and the obtained suspension of sodium salts
RUSSIAN JOURNAL OF BIOORGANIC CHEMISTRY Vol. 32 No. 6 2006

556
KUR’YANOV et al.
Table 4. Bond lengths (Å) in crystal of (V)
was treated with chloride (I) (0.5 g, 1.37 mmol) and
15C5 (0.054 ml, 0.274 mmol), and stirred at room tem-
perature until the full conversion of the glycosyl donor
(TLC). Solids were filtered off, the filtrate was evapo-
rated to dryness at a reduced pressure, and products (V)
and (VI) were separated b a column chromatography.
3-N-(2-Acetamido-3,4,6-tri-O-acetyl-2-deoxy-b-
D-glucopyranosyl)-benzoxazol-2-one (V); mp 187–
189°ë, [α]546 –71° (c 1.0, chloroform).
3-N-(2-Acetamido-3,4,6-tri-O-acetyl-2-deoxy-b-
D-glucopyranosyl)-5-methylbenzoxazol-2-one (VI);
mp 178–180°ë, [α]546 –75° (Ò 1.0, chloroform).
3-N-(2-Acetamido-3,4,6-tri-O-acetyl-2-deoxy-b-
D-glucopyranosyl)benzothiazol-2-one (VII); mp
179–181°ë, [α]546 –81° (Ò 1.0, chloroform).
N1–C13
N2–C6
1.367 (7)
1.373 (6)
1.441 (6)
1.431 (6)
1.357 (6)
1.218 (7)
1.425 (6)
1.366 (7)
1.206 (8)
1.427 (6)
1.529 (7)
1.517 (7)
1.498 (7)
1.388 (7)
1.368 (9)
1.374 (7)
1.487 (8)
1.476 (8)
N1–C2
1.438 (6)
1.386 (6)
1.399 (5)
1.211 (6)
1.379 (6)
1.371 (6)
1.193 (7)
1.432 (6)
1.353 (6)
1.191 (6)
1.522 (7)
1.518 (7)
1.382 (8)
1.356 (9)
1.413 (8)
1.480 (8)
1.477 (9)
N2–C12
O1–C1
N2–C1
O1–C5
O2–C6
O3–C7
O3–C6
O4–C13
O5–C3
O5–C15
O6–C15
O7–C4
O7–C17
O8–C17
O9–C19
C1–C2
O9–C20
O10–C20
C2–C3
C3–C4
C4–C5
C5–C19
C7–C12
C9–C10
C11–C12
C15–C16
C20–C21
C7–C8
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C6–N2–C1
C1–O1–C5
C15–O5–C3
C20–O9–C19
C20–O9–C19
N1–C2–C3
C3–C2–C1
122.5 (5) C6–N2–C12
122.2 (4) C12–N2–C1
113.9 (3) C7–O3–C6
117.1 (4) C17–O7–C4
116.9 (4) O1–C1–N2
116.9 (4) O1–C1–N2
109.7 (4) N1–C2–C1
111.3 (4) O5–C3–C4
108.5 (4) C4–C3–C2
105.7 (4) O7–C4–C5
109.4 (4) O1–C5–C19
109.1 (4) C19–C5–C4
129.0 (5) O2–C6–O3
108.0 (5) O3–C7–C8
110.0 (4) C8–C7–C12
116.8 (6) C8–C9–C10
108.8 (4)
127.8 (4)
107.4 (4)
118.5 (5)
107.4 (4)
107.4 (4)
110.0 (4)
108.8 (4)
110.9 (4)
110.3 (4)
106.8 (4)
112.9 (4)
122.9 (5)
127.9 (5)
122.1 (5)
122.5 (5)
O5–C3–C2
O7–C4–C3
C3–C4–C5
O1–C5–C4
O2–C6–N2
N2–C6–O3
O3–C7–C12
C9–C8–C7
C9–C10–C11
C11–C12–N2
N2–C12–C7
O4–C13–C14
O6–C15–O5
O5–C15–C16
O8–C17–C18
O9–C19–C5
121.3 (6) C12–C11–C10 116.2 (5)
133.3 (5) C11–C12–C7
105.6 (4) O4–C13–N1
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123.1 (5) O6–C15–C16
110.6 (5) O8–C17–O7
126.9 (6) O7–C17–C18
108.8 (4) O10–C20–O9
121.1 (4)
122.9 (5)
114.7 (6)
126.4 (5)
121.9 (6)
111.1 (7)
123.1 (5)
111.2 (4)
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