Macrocyclic ammonio-N-nitroimines

Article abstract of DOI:10.1023/A:1012447104776

Condensation of 4,5-bis(chloromethyl)-1-methyl-1,2,3-triazole with polyethylene glycols and polyethylenepolyamines gave crown-ethers and azacrown compounds which were converted into the corresponding N-nitroimines.

Full text of DOI:10.1023/A:1012447104776

Russian Journal of Organic Chemistry, Vol. 37, No. 7, 2001, pp. 1038 1045. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 7, 2001,
pp. 1086 1092.
Original Russian Text Copyright
2001 by Vyazkov, Shitov, Tartakovskii.
Macrocyclic Ammonio-N-nitroimines
V. A. Vyazkov, O. P. Shitov, and V. A. Tartakovskii
Zelinskii Institut of Organic Chemistry, Russian Academy of Sciences,
Leninskii pr. 47, Moscow, 117913 Russia
Mari El State University, pl. Lenina 1, Ioshkar-Ola, 424001 Mari El, Russia
Received June 10, 1999
Abstract Condensation of 4,5-bis(chloromethyl)-1-methyl-1,2,3-triazole with polyethylene glycols and poly-
ethylenepolyamines gave crown-ethers and azacrown compounds which were converted into the corresponding
N-nitroimines.
A great number of publications on the synthesis
and properties of macrocyclic compounds deals with
those containing oxygen and nitrogen as heteroatoms.
N-Nitroimides derived from crown compounds were
not reported, though their synthesis undoubtedly
attracts attention from the viewpoint of structural
modification. Two approaches to the synthesis of such
macrocycles are possible: (1) cyclization of func-
tionally substituted ammonio-N-nitroimides with salts
derived from polyethylene glycols or linear poly-
ethylenepolyaza compounds (Scheme 1) and (2) intro-
duction of an N-nitroimide fragment to nitrogen atom
of a heterocycle fused with crown ether (Scheme 2).
[1, 2, 3]. In the synthesis of polyaza macrocycles
aliphatic dihalogen derivatives can be used instead of
p-toluenesulfonates [3, 4] (Scheme 3).
The condensation of 4,5-bis(chloromethyl)-1-
methyl-1,2,3-triazol-3-io-N-nitroimide (I) with 1,4,7-
tritosyl-1,4,7-triazaheptane in the presence of potas-
sium carbonate and benzyltriethylammonium chloride
as catalyst gave the corresponding N-nitroimide II in
only 4% yield. The major product was compound III
(Scheme 4); its formation indicates easy elimination
of the nitroimide fragment by the action of bases.
Therefore, we examined another approach, according
to which aza crown ether III was initially obtained
from 4,5-bis(chloromethyl)-1-methyl-1,2,3-triazole
(IV) (Scheme 5). The optimal reaction temperature
was 70 80 C. At lower temperature, linear products
Aza macrorings are synthesized mainly by cycliza-
tion of N-tosyl derivatives of linear polyamines with
diol bis(p-toluenesulfonates) in the presence of bases
Scheme 1.
B = O, NTs.
Scheme 2.
1070-4280/01/3707-1038$25.00 2001 MAIK Nauka/Interperiodica

MACROCYCLIC AMMONIO-N-NITROIMINES
1039
Scheme 3.
are formed, while heating above that temperature
leads to decomposition of the initial compound. By
amination of III with hydroxylamine O-picryl ether
(NH2OPic) in methylene chloride we obtained the cor-
responding 3-aminotriazolium picrate V, and the latter
was treated with nitronium tetrafluoroborate in dry
acetonitrile. As a result, we isolated N-nitroimide II
with mp 200 C. Our studies have shown that in the
presence of excess NO2BF4 both deamination of V
and removal of tosyl groups from II occur. There-
fore, the nitration should be carried out with a stoi-
chiometric amount of nitronium tetrafluoroborate, and
Scheme 4.
Scheme 5.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 7 2001

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VYAZKOV et al.
Scheme 6.
the temperature should not exceed 15 C. Compound
II is the first representative of N-nitroimides in the
aza crown ether series.
with Na+ and K+ ions [1]. According to the data of
[5], high-temperature syntheses of crown ethers
(heating above 80 C) often result in reduced yields
of the target products. The optimal temperature was
proposed to be 60 C. Under these conditions, the reac-
tion takes 4 h, and a number of halogen derivatives
can be involved (Scheme 7).
We have studied the condensation of bis(chloro-
methyl)triazole IV with tetraethylene glycol in di-
oxane at 60 C and found that the reaction takes 3 h in
the presence of Li, Na+, or K+ ions. In all cases prod-
uct X was isolated as a thick brown oil (Scheme 8).
In the presence of lithium and potassium cations the
yield of X was lower (30 40%) than in the presence
of sodium cation (60%). Our attempts to improve
the procedure for preparation of compound X by
using 4,5-bis(hydroxymethyl)-1-methyl-1,2,3-triazole
instead of IV were unsuccessful: the yield of product
X did not exceed 50%. Crown ether X gives no
Next we planned to synthesize a macrocyclic com-
pound having two N-nitroimide fragments. For this
purpose, bis(chloromethyl)triazole IV was brought
into reaction with diamine VI which was synthesized
from IV according to Scheme 6. The reaction was
carried out at 70 C, and in 2 h we obtained cyclic
product VIII as a mixture of two isomers. Amination
of VIII with excess hydroxylamine O-picryl ether
in methylene chloride gave isomeric picrates IX
which were treated with nitronium tetrafluoroborate
in acetonitrile. As a result, we isolated a mixture
of initial amino derivatives IX as tetrafluoroborates
(Scheme 6). We failed to obtain the desired N-nitro-
imino derivatives by repeated nitration of these salts.
It is known [1, 4, 5] that crown ethers are usually
synthesized in dioxane or diethylene glycol dimethyl
ether as solvent, making use of matrix effects of alkali molecular ion peak in the mass spectrum, and only
metal cations which fit the cavity of the crown ether
being formed. The best results are usually obtained
fragment ion peaks with m/z 286 and 287 (formed
by elimination of CH3) and those resulting from
Scheme 7.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 7 2001

MACROCYCLIC AMMONIO-N-NITROIMINES
1041
Scheme 8.
elimination of CH2CH2O are observed. The amination
molecular weight determined experimentally was con-
sistent with the calculated value. No molecular ion
peak was found in the mass spectrum of XIII, but
a strong peak with m/z (I = 28 rel. units) was ob-
served, which suggests easy decomposition of crown
of X with hydroxylamine O-picryl ether in anhydrous
1
methylene chloride afforded picrate XI. Its H NMR
spectrum contained a multiplet at 3.67 ppm from
the polyether ring protons and singlets at 4.41 and
5.05 ppm from the methylene group protons. These
data indicate that only one isomer is formed. Also,
signals from the picrate ion ( 8.67 ppm) and methyl
group ( 4.58 ppm) were present. The nitration of XI
with NO2BF4 gave N-nitroimide XII with mp 140 C
(Scheme 8); compound XII is the first stable N-nitro-
imide in the crown ether series. The product is capable
of forming various complexes with alkali metal
cations, which made its purification and identification
difficult.
By cyclization of dichloride IV with 4,5-bis-
(hydroxymethyl)-1-methyl-1,2,3-triazole in the pres-
ence of NaOH we tried to synthesize a crown ether
having several N-nitroimide fragments. As a result,
we obtained product XIII in 30% yield (Scheme 9).
The yield of the product was increased when 4,5-bis-
(chloromethyl)-1-methyl-1,2,3-triazole (IV) alone
was used. The maximal yield of XIII was 60%. Its
1
ether XIII with formation of diradical A. The H
NMR spectrum of XIII contained singlets at 3.94,
4.59, and 4.62 ppm from the methyl and methylene
groups, respectively; these data indicate a symmetrical
structure of the product. Taking into account that the
CH2Cl groups in the initial compound are nonequiv-
alent and hence the energies of the C Cl bonds are
not similar, the 1,3:1,3 isomer seems to be preferred.
This assumption is also confirmed by the fact that the
resulting crown ether reacts with a stoichiometric
amount of hydroxylamine O-picryl ether to form
diamino derivative XIV as a mixture of two isomers
(Scheme 10); product XIV was isolated by treatment
of the reaction mixture with pentane.
In the presence of a 20% excess of NH2OPic we
obtained 50% of tetrapicrate XV, and the amination
took no less than 10 h, presumably because of steric
effect of the amino groups being introduced. The
Scheme 9.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 7 2001

1042
VYAZKOV et al.
Scheme 10.
subsequent nitration of XV with a stoichiometric
amount of nitronium tetrafluoroborate gave tetra-N-
nitroimide XVI. We failed to raise the yield of XVI
by increasing the amount of the nitrating agent.
N-Nitroimide XVI is a low-melting substance,
mp 110 C.
imide (II). To a suspension of 0.3 g of compound IV
in 20 ml of anhydrous acetonitrile we added with
stirring at 10 C 0.04 g of NO2BF4 in portions. The
mixture was stirred for 30 min at 10 C, 50 mg of
anhydrous K2CO3 was added, and the mixture was
stirred for 1 h at 0 C and filtered. The precipitate was
washed with 5 ml of chloroform, the filtrate was
combined with the washings and was evaporated to
dryness under reduced pressure (10 mm, bath tem-
perature <40 C), and the residue was recrystallized
from acetonitrile. Yield 0.1 g (40%), mp 219 220 C
EXPERIMENTAL
The IR spectra were recorded on a Specord 75-IR
spectrometer. The 13C NMR spectra were measured
1
1
on a Bruker-250 instrument, and the H NMR spectra,
(decomp.). IR spectrum (KBr), , cm : 1150, 1320,
1
on a Jeol-90 spectrometer (90 MHz). The mass spe-
ctra were run on a Varian-XC spectrometer.
14-Methyl-3,6,9-tritosyl-3,6,9,12,13,14-hexaaza-
bicyclo[9.3.0]tetradeca-1(11),12-dien-12-io-12-nitro-
1600, 1250, 1440, 1460, 1640, 2920, 3100. H NMR
spectrum (DMSO-d6), , ppm: 2.53 s (CH3), 2.6 s
(2CH3), 3.17 s (2CH2), 3.36 s (2CH2), 4.65 s (CH3),
4.87 s (CH2), 5.17 s (CH2), 7.6 m (8CH), 7.8 m
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 7 2001

MACROCYCLIC AMMONIO-N-NITROIMINES
1043
(4CH). Found, %: C 50.07; H 5.13; N 15.74; S 12.82.
C30H36N8O8S3. Calculated, %: C 49.18; H 4.90;
N 15.26; S 13.08.
was filtered off, washed with pentane, and dried in air.
Yield 0.6 g (90%), mp 244 245 C (decomp.). IR
spectrum (KBr), , cm : 1070, 1160, 1280, 1340,
1
1440, 1490, 1510, 1560, 1610, 1630, 3100, 3550,
14-Methyl-3,6,9-tritosyl-3,6,9,12,13,14-hexaaza-
bicyclo[9.3.0]tetradeca-1(11),12-diene (III). a. To
a solution of 1.2 g of benzyltriethylammonium
chloride in 60 ml of DMF we added with stirring
1.2 g of anhydrous K2CO3 and 3.6 g 1,4,7-tritosyl-
1,3,7-triazaheptane. The mixture was stirred for
20 min at 20 C and heated to 40 C, a solution of
1.2 g of 4,5-bis(chloromethyl)-1-methyl-1,2,3-triazole
(IV) in 10 ml of DMF was added over a period of
15 min, and the mixture was stirred for 2 h at 50 C
and for 2 h at 80 C, cooled, and filtered. The filtrate
was evaporated under reduced temperature (10 mm,
bath temperature 70 C) to 1/3 of the initial volume,
100 ml of distilled water was added to the residue,
and the precipitate was filtered off, washed with
water, recrystallized from acetone, and dried in air.
Yield 2.5 g (56%), mp 210 211 C. IR spectrum
1
3620. H NMR spectrum (acetone-d6), , ppm: 2.5 s
(3CH3), 3.15 s (2CH2), 3.6 s (2CH2), 4.6 s (CH3),
4.75 s (CH2), 5.03 s (CH2), 6.3 br.s (NH2), 7.6 m
(8CH), 7.8 m (4CH), 8.6 s (2CH). Found, %: C 46.80;
H 4.36; S 9.99. C36H40N10O13S3. Calculated, %:
C 47.10; H 4.37; S 10.46.
4,5-Bis(aminomethyl)-1-methyl-1,2,3-triazole
(VI). A solution of 0.6 g of dichloride IV in 5 ml of
chloroform was added dropwise with stirring at 20 C
to a solution of 2 ml of 30% NH4OH in 10 ml of
alcohol. The mixture was heated under reflux for 1 h,
cooled, kept for 14 h at 20 C, and filtered, and the
filtrate was evaporated to dryness under reduced
pressure (10 mm, bath temperature 50 C). The residue
was dissolved in 5 ml of dioxane, the solution was
filtered, 20 ml of methylene chloride was added to
the filtrate, the precipitate was filtered off, the filtrate
was evaporated to dryness under reduced pressure
(10 mm), and the residue was dried in a vacuum
(1 mm) for 1 h. Product VI was isolated as an oily
substance. Yield 0.4 g (85%). IR spectrum (KBr), ,
1
(KBr), , cm : 1090, 1170, 1340, 1450, 1500, 1610,
1
1670, 2850, 2970. H NMR spectrum (CDCl3),
,
ppm: 2.4 s (CH3), 2.5 s (2CH3), 3.1 m (2CH2),
3.53 m (2CH2), 4.29 s (CH2), 4.36 s (CH3), 4.58 s
(CH2), 7.6 m (4CH), 7.8 m (8CH). Found, %:
C 53.18; H 5.68; N 12.65; S 13.46. C30H36N6O6S3.
Calculated, %: C 53.57; H 5.36; N 12.50; S 14.28.
b. To a solution of 0.15 g of benzyltriethylammo-
nium chloride in 10 ml of DMF we added with stir-
ring 0.1 g of anhydrous K2CO3 and 0.4 g of 1,4,7-tri-
tosyl-1,3,7-triazaheptane. The mixture was heated to
50 C, and a solution of 0.2 g of dichloride I in 10 ml
of DMF was added dropwise with vigorous stirring.
The mixture was stirred for 1 h at 50 C and for 2 h at
80 C, cooled, and filtered, the filtrate was evaporated
1
1
cm : 1090, 1160, 1450, 1640, 2900, 3300. H NMR
spectrum (CDCl3), , ppm: 4.0 s (CH3), 4.60 s
(2CH2), 6.5 br.s (NH2).
1-Methyl-4,5-bis(tosylaminomethyl)-1,2,3-tri-
azole (VII). A solution of 0.7 g of compound VI and
0.5 g of NaOH in 7 ml of distilled water was added
dropwise over a period of 30 min to a solution of
2.5 g of p-toluenesulfonyl chloride in 20 ml of diethyl
ether, vigorously stirred at 20 C. The mixture was
stirred for 2 h at 20 C and was left to stand for 10 h
under reduced pressure (10 mm, bath temperature at 20 C, the solution was separated from the precip-
70 C) to 1/3 of the initial volume, 50 ml of distilled
water was added, and the precipitate was filtered off,
washed with 50 ml of water, reprecipitated twice from
acetone with water, and dried in air. Yield 0.32 g
(57%), mp 200 203 C (no depression of the melting
point was observed on mixing with a sample obtained
as described in a). The IR spectra of the products
obtained by methods a and b were identical.
12-Amino-14-methyl-3,6,9-tritosyl-3,6,9,12,13,14-
hexaazabicyclo[9.3.0]tetradeca-1(11),12-dien-12-
ium picrate (V). To a solution of 0.2 g of hydroxyl-
amine O-picryl ether in 40 ml of chloroform we added
with stirring at 20 C a solution of 0.5 g of compound
III in 10 ml of chloroform. The mixture was stirred
for 1 h at 20 C and for 1 h at 40 C. It was then
cooled, the precipitate was filtered off, 15 ml of
pentane was added to the filtrate, and the precipitate
itate by decanting, and the precipitate was washed
with water until neutral washings and with ether until
complete crystallization. The precipitate was dissolved
in chloroform and reprecipitated with ether. Yield
0.8 g (65%), mp 134 136 C. IR spectrum (KBr), ,
1
cm : 1090, 1170, 1340, 1450, 1500, 1600, 1640,
1
3000, 3400. H NMR spectrum (CDCl3), , ppm:
2.3 s (2CH3), 4.1 s (CH3), 4.65 s (2CH2), 7.5 m
(8CH). Found, %: C 51.51; H 5.61. C19H23N5O4S2.
Calculated, %: C 50.79; H 5.12.
6,14-Dimethyl-3,11-ditosyl-3,6,7,8,11,14,15,16-
octaazatricyclo[11.3.0.05,9]hexadeca-1(13),5(9),7,15-
tetraene (VIII). Finely powdered anhydrous K2CO3,
0.19 g, was added with stirring at 20 C to a solution
of 0.35 g of compound VII and 0.19 g of benzyltri-
ethylammonium chloride in 10 ml of DMF. The mix-
ture was stirred for 15 min at 20 C and heated to
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VYAZKOV et al.
40 C, and a solution of 0.18 g of compound I in 5 ml
of DMF was added over a period of 10 min. The
mixture was kept for 4 h at 70 C, cooled, and poured
into 30 ml of distilled water, and the precipitate was
filtered off, washed with 3 5 portions of water, and
dried in air. The product was purified by reprecipita-
tion from acetonitrile with chloroform. Yield 0.26 g
b. To a solution of 0.3 g of tetraethylene glycol
in 15 ml of dioxane at 20 C we added 0.27 g of
sodium hydroxide, the mixture was stirred for 30 min
at 20 C, a solution of 0.3 g of compound IV in 5 ml
of dioxane was added over a period of 15 min, and
the mixture was stirred for 4 h at 50 C and cooled.
The precipitate was filtered off and washed with 5 ml
of dioxane, the filtrate was evaporated to dryness
under reduced pressure (10 mm, bath temperature
50 C), 5 ml of distilled water was added to the
residue, and the product was extracted into methylene
chloride (3 5 ml). The combined extracts were dried
over magnesium sulfate and evaporated to dryness.
Compound X was isolated as a yellow oily substance.
1
(58%), mp 176 178 C. IR spectrum (KBr), , cm :
1080, 1330, 1430, 1460, 1590, 1620, 2930, 3060.
1H NMR spectrum (CDCl3), , ppm: 2.3 s (2CH3),
3.85 s (2CH3), 4.45 s (2CH2), 4.6 s (2CH2), 7.5 m
(8CH). Found, %: C 51.94; H 5.79. C24H28N8O4S2.
Calculated, %: C 51.79; H 5.36.
6,14-Diamino-8,16-dimethyl-3,11-ditosyl-3,6,7,-
8,11,14,15,16-octaazatricyclo[11.3.0.05,9]hexadeca-
1(13),5(9),7,15-tetraene-6,14-diium dipicrate (IX).
A solution of 0.25 g of compound VIII in 30 ml of
dry methylene chloride was added with stirring at
20 C to a solution of 0.25 g of hydroxylamine
O-picryl ether in 30 ml of dry methylene chloride.
The mixture was stirred for 4 h at 20 C and was left
to stand for 10 h at 20 C, 10 ml of pentane was
added, and the precipitate was filtered off and recrys-
tallized from aqueous alcohol. Yield 0.35 g (70%),
1
Yield 0.3 g (60%). IR spectrum (KBr), , cm : 1100,
1
1250, 1280, 1350, 1450, 1620, 2880. H NMR spec-
trum (CDCl3), , ppm: 3.6 m (8CH2), 3.97 s (CH3),
4.73 s (CH2), 4.83 s (CH2). Mass spectrum (70 eV),
m/z (I, rel. units): 300 (2); 296 (16); 251, 252 (18);
207, 208 (17); 163, 164 (22); 44 (28); 15 (27). Found,
%: C 52.42; H 6.78. C13H23N3O5. Calculated, %:
C 52.00; H 7.66.
18-Amino-20-methyl-3,6,9,12,15-pentaoxa-
18,19,20-triazabicyclo[15.3.0]eicosa-1(17),18-dien-
18-ium picrate (XI). a. A solution of 0.25 g of
compound X in 5 ml of chloroform was added at
20 C to a solution of 0.25 g of hydroxylamine
O-picryl ether in 20 ml of chloroform. The mixture
was stirred for 2 h at 20 C and was left to stand for
10 h, 10 ml of pentane was added, and the tarry
precipitate was filtered off and recrystallized from
alcohol. Yield 0.3 g (60%), mp 109 C (decomp.). IR
mp 198 200 C (decomp.). IR spectrum (KBr),
,
1
cm : 1080, 1150, 1330, 1420, 1450, 1350, 1560,
1
1600, 1640, 2950, 3100, 3150, 3350. H NMR spec-
trum (DMSO-d6), , ppm: 2.3 s (2CH3), 4.05 s
(2CH3), 4.55 s (2CH2), 4.7 s (2CH2), 7.55 m (8CH),
8.6 s (4CH). Found, %: C 41.99; H 4.60; S 6.07.
C36H36N16O18S2. Calculated, %: C 41.38; H 3.44;
S 6.13.
1
18-Methyl-3,6,9,12,15-pentaoxa-18,19,20-triaza-
bicyclo[15.3.0]eicosa-1(17),19-diene (X). a. Potas-
sium hydroxide, 0.32 g, was added at 20 C to a solu-
tion of 0.4 g of 4,5-bis(hydroxymethyl)-1-methyl-
1,2,3-triazole in 30 ml of DMF. The mixture was
stirred for 10 min at 20 C, 1.5 g of tetraethylene
glycol bis(p-toluenesulfonate) was added, and the
mixture was heated under stirring to 60 C, stirred for
2 h at that temperatire, cooled, and evaporated under
reduced pressure (10 mm, bath temperature 70 C) to
1/4 of the initial volume. Diethyl ether, 20 ml, was
added to the residue, and the precipitate was filtered
off, the filtrate was evaporated to dryness under
reduced pressure (10 mm, water bath), 10 ml of dis-
tilled water was added to the residue, and the product
was extracted into chloroform (3 5 ml). The com-
bined extracts were dried over magnesium sulfate and
evaporated to dryness, and the residue was dried under
reduced pressure (10 mm, bath temperature 50 C) for
1 h. Compound X was isolated as a yellow oily sub-
stance, yield 0.5 g (50%).
spectrum (KBr), , cm : 1070, 1150, 1265, 1310
1360, 1430, 1500, 1540, 1620, 2900, 3100, 3400.
1H NMR spectrum (acetone-d6), , ppm: 8.62 s
(2CH), 6.5 br.s (NH2), 5.05 s (CH2), 4.41 s (CH2),
3.58 s (CH3), 3.67 m (8CH2). Found, %: C 41.43;
H 3.87. C19H25N7O12. Calculated, %: C 41.83; H 4.95.
20-Methyl-3,6,9,12,15-pentaoxa-18,19,20-triaza-
bicyclo[15.3.0]eicosa-1(17),18-dien-18-io-18-nitro-
imide (XII). Nitronium tetrafluoroborate, 0.23 g, was
added in portions with stirring at 10 C to a solution
of 0.5 g of compound XI in 20 ml of anhydrous
acetonitrile. The mixture was stirred for 30 min at
10 C, 0.15 g of anhydrous K2CO3 was added, the
mixture was stirred for 30 min at 0 C, the precipitate
was filtered off, and the filtrate was evaporated to
dryness under reduced pressure (10 mm, bath tem-
perature <40 C). The residue was washed with 20 ml
of hot water, reprecipitated from acetonitrile with
ether, and dried in air. Yield 0.07 g (25%), mp 142
1
143 C. IR spectrum (KBr), , cm : 1270, 1440
(NNNO2). 1H NMR spectrum (CD3CN), , ppm: 4.1 s
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MACROCYCLIC AMMONIO-N-NITROIMINES
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(CH3), 4.8 s (CH2), 4.88 s (CH2), 3.68 m (8CH2).
Found, %: C 43.39; H 6.87; N 18.74. C13H23N5O7.
Calculated, %: C 43.21; H 6.37; N 19.39.
was added at 20 C to a solution of 2 g of hydroxyl-
amine O-picryl ether in 200 ml of methylene chloride.
The mixture was stirred for 2 h at 20 C and was left
overnight, and the precipitate was filtered off, recrys-
tallized from alcohol, and dried under reduced pres-
sure (10 mm) for 1 h. Yield 1.5 g (50%), mp 169
6,16,22,32-Tetramethyl-3,11,19,27-tetraoxa-6,7,-
8,14,15,16,22,23,24,30,31,32-dodecaazapentacyclo-
[27.3.0.05,9.013,17.021,25]dotriaconta-1(29),5(9),7,-
13(17),14,21(25),23,30-octaene (XIII). A solution of
3 g of compound IV in 10 ml of dioxane was added
over a period of 20 min to a suspension of 2 g of
sodium hydroxide in 40 ml of dioxane, vigorously
stirred at 40 C. The mixture was stirred for 4 h at
60 C and cooled, the precipitate was filtered off,
the filtrate was evaporated to dryness under reduced
pressure (10 mm, bath temperature 50 C), 10 ml of
distilled water was added to the residue, and the prod-
uct was extracted into methylene chloride (2 10 ml).
The extract was dried over magnesium sulfate and
1
170 C (decomp.). IR spectrum (KBr), , cm : 3100,
3300, 1640, 1610, 1550, 1340, 1320, 1260, 1150,
1
1080. H NMR spectrum (CD3CN), , ppm: 4.3 s
(4CH3), 5.3 s (4CH2), 6.5 br.s (NH2), 5.35 s
(4CH2), 8.54 s (8CH). Found, %: C 35.27; H 2.99.
C44H44N28O28. Calculated, %: C 35.50; H 2.97.
6,16,22,32-Tetramethyl-3,11,19,27-tetraoxa-6,7,-
8,14,15,16,22,23,24,30,31,32-dodecaazapentacyclo-
[27.3.0.05,9.013,17.021,25]dotriaconta-1(29),5(9),7,-
13(17),14,21(25),23,30-octaene-8,14,24,30-tetraio-
8,14,24,30-tetrakis(nitroimide) (XVI). Nitronium
evaporated to dryness, and the residue was evacuated tetrafluoroborate, 0.16 g, was added in portions to
for 1 h (1 mm). Compound XIII was isolated as
a suspension of 0.5 g of compound XV in 10 ml of
anhydrous acetonitrile, stirred at 10 C. The mixture
was stirred for 1 h at 10 C, 0.2 g of potassium
carbonate was added, and the mixture was stirred for
1 h at 5 C and filtered. The filtrate was evaporated
to dryness, and the residue was reprecipitated from
acetonitrile with ether and dried in air. Yield 0.1 g
(50%), mp 110 C (decomp.). IR spectrum (KBr), ,
cm : 1270 1280, 1420, 1110, 3100. H NMR spec-
trum (CD3CN), , ppm): 4.4 s (4CH3), 5.32 s
(4CH2), 5.47 s (4CH2). Found, %: C 32.60; H 3.7.
C20H28N20O12. Calculated, %: C 32.43; H 3.78.
Determination of the molecular weight of crown
ether XIII. a. Rast procedure. Camphor was used as
reference, mp 177 C (0.8 g); sample weight 0.051 g.
T 5.5 C. Mcalc 463.
b. From refractive index. Acetonitrile was used as
reference, d = 0.78 g/ml, n2D2 = 1.3412. Crown ether,
d = 1.2 g/ml, n2D2 = 1.5488. A solution of crown ether
in acetonitrile (1:10), d = 0.87 g/ml, n2D2 = 1.3540.
Calculation by the Lorentz Lorentz formula assuming
refraction additivity gave M = 482.
a yellow oily substance. Yield 1.25 g (70%). IR spec-
1
trum (KBr), , cm : 1070, 1100, 1240, 1380, 1440,
1
1470, 1650, 2850, 2950. H NMR spectrum (CDCl3),
, ppm: 3.94 s (4CH3), 4.59 s (4CH2), 4.62 s (4CH2).
13C NMR spectrum (CDCl3), C, ppm: 30.721 (CH3),
34.76 and 34.90 (CH2), 131.158 and 142.069 (C).
Mass spectrum, m/z (I, rel. units): 125 (37), 110 (42),
15 (39). M 470.
1
1
8,30(or 8,24)-Diamino-6,16,22,32-tetramethyl-
3,11,19,27-tetraoxa-6,7,8,14,15,16,22,23,24,30,31,32-
dodecaazapentacyclo[27.3.0.05,9.013,17.021,25]dotria-
conta-1(29),5(9),7,13(17),14,21(25),23,30-octaene-
8,30(or 8,24)-diium dipicrate (XIV). A solution of
1 g of compound XIII in 50 ml of methylene chloride
was added at 20 C to a solution of 2 g of hydroxyl-
amine O-picryl ether in 150 ml of methylene chloride.
The mixture was stirred for 2 h, 100 ml of pentane
was added, and the precipitate was filtered off, recrys-
tallized from methylene chloride, and dried under
reduced pressure (10 mm, bath temperature 40 C) for
1 h. Yield 1.5 g (75%), mp 117 119 C. IR spectrum
1
(KBr), , cm : 3100, 3300, 1640, 1610, 1550, 1340,
1320, 1250, 1140, 1080. 1H NMR spectrum (CD3CN),
, ppm: 4.0 d (4CH3), 4.3 d (4CH3), 4.6 d (2CH2),
4.7 d (2CH2), 5.2 d (2CH2), 5.3 d (2CH2), 8.6 s
(8CH), 5.7 br.s (2NH2). Found, %: C 39.27; H 3.61;
N 20.85. C32H36N20O18. Calculated, %: C 38.86;
H 3.64; N 21.45.
REFERENCES
1. Hiraoka, M., Crown Compounds. Their Characteristics
and Applications, Tokyo: Kodansha, 1982.
2. Pedersen, C.D. and Frensdorf, H.C., Usp. Khim., 1973,
vol. 42, no. 3, p. 493.
3. Luk’yanenko, N.G., Basok, S.C., and Filonova, L.K.,
8,14,24,30-Tetraamino-6,16,22,32-tetramethyl-
3,11,19,27-tetraoxa-6,7,8,14,15,16,22,23,24,30,31,32-
dodecaazapentacyclo[27.3.0.05,9.013,17.021,25]dotria-
conta-1(29),5(9),7,13(17),14,21(25),23,30-octaene-
8,14,24,30-tetraium tetrapicrate (XV). A solution of
1 g of compound XIII in 50 ml of methylene chloride
Zh. Org. Khim., 1988, vol. 24, no. 8, p. 1731.
4. Chavez, F. and Sherry, I.D., J. Org. Chem., 1989,
vol. 54, p. 2990.
5. Kawamura, N., Miki, M., Ikeda, I., and Okahara, M.,
Tetrahedron Lett., 1979, no. 6, p. 535.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 7 2001