2,2-Bis(methoxy- and ethoxy-NNO-azoxy)propane-1,3-diol sulfonates

Article abstract of DOI:10.1134/S1070428014050030

2,2-Bis(alkoxy-NNO-azoxy)propane-1,3-diols react with sulfonyl chlorides and trifluoromethanesulfonic anhydride in the presence of bases affording previously unknown methane-, trifluoromethane-, benzene and toluenesulfonates (sulfonic esters) of 2-bis(met

Full text of DOI:10.1134/S1070428014050030

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 5, pp. 631–634. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © I.N. Zyuzin, 2014, published in Zhurnal Organicheskoi Khimii, 2014, Vol. 50, No. 5, pp. 646–649.
2,2-Bis(methoxy- and Ethoxy-NNO-azoxy)propane-1,3-diol
Sulfonates
I. N. Zyuzin
Institute of Problems of Chemical Physics, Russian Academy of Sciences,
pr. Akademika Semenova 1, Chernogolovka, Moscow obl., 142432 Russia
e-mail: zyuzin@icp.ac.ru
Received October 2, 2013
Abstract—2,2-Bis(alkoxy-NNO-azoxy)propane-1,3-diols react with sulfonyl chlorides and trifluoromethane-
sulfonic anhydride in the presence of bases affording previously unknown methane-, trifluoromethane-, benzene
and toluenesulfonates (sulfonic esters) of 2-bis(methoxy- and ethoxy-NNO-azoxy)propane-1,3-diols. The triflates
are thermally less stable than mesylates, benzenesulfonates, and tosylates of the corresponding diols.
DOI: 10.1134/S1070428014050030
Alkoxy-NNO-azoxy compounds have been known
since the end of nineteenth century [1, 2]. Their
preparation methods along with the other azoxy
compounds are summarized in reviews [3–5]. Some
specimens of this class compounds were considered
among biologically active substances [5–7] and
components of energetic materials [8, 9]. Among the
alkoxy-NNO-azoxy compounds bis(methoxy-NNO-
azoxy)-methane and its homologs are the most
accessible [2, 10], although the introduction of two
geminal alkoxyazoxy group is insufficiently selective
[2, 11]. In turn, 2,2-bis(alkoxy-NNO-azoxy)propane-
1,3-diols that easily and in high yields are formed in
reactions of bis(alkoxy-NNO-azoxy)-methanes with
formaldehyde [12–14] can be regarded as the most
available functionally substituted alkoxy-NNO-azoxy
compounds. Besides, 2,2-bis(methoxy-NNO-azoxy)
propane-1,3-diol (I) always formed as a side product in
the synthesis of 2,2-bis(methoxy-NNO-azoxy)ethanol
[13, 14], the key starting compound for the preparation
of 1,1-bis(methoxy-NNO-azoxy)ethene [13], and for
the introduction of 2,2-bis(methoxy-NNO-azoxy)ethyl
group in various molecules [15–17]. Therefore an
urgent task is the utilization of diol I providing as a
result new energetic substances. The functionalization
of the hydroxy groups of 2,2-bis-(alkoxy-NNO-azoxy)
propane-1,3-diols afforded formerly nitro and acetyl
derivatives [18], and also cyclic sulfites [19]. The only
known sulfonate of 2-(alkoxy-NNO-azoxy)alcohols is
the 2,2-bis(methoxy-NNO-azoxy)ethanol mesylate
[13].
In this study the previously unknown 2,2-bis-
(alkoxy-NNO-azoxy)-propane-1,3-diol sulfonates were
synthesized (Scheme 1).
Mesylates IVа and Vа were obtained in nearly
quantitative yields. Some decrease in the yield of
sulfonates IVb–IVd and Vb–Vd was apparently due to
the higher rate of hydrolysis, especially of triflates IVb
and Vb, compared with the mesylates and,
consequently, to larger losses at the extraction. Besides
the higher solubility of sulfonates IVb–IVd and Vb–
Vd as compared with mesylates IVа and Vа might
increase the losses during the recrystallization. The
synthesis of sulfonic esters from alcohols and sulfonyl
chlorides is often accompanied with the side formation
of olefins, ethers, and chloroalkanes [20]. However,
according to TLC data only the target sulfonic esters
were present. This is apparently due to the high
Scheme 1.
O
O
OR
OR
R1SO2O
R1SO2O
N
N
N
N
N
N
N
N
HO
HO
B
R1SO2Cl
OR
OR
O
O
I, II
IIIa-IIId
IVa–IVd, Va–Vd
R = Me (I, IV), Et (II, V); R1 = Me (a), CF3 (b), Ph (c), 4-
MeC6H4 (d); B = Et3N, i-Pr2NEt, 2,6-Me2Py.
631

ZYUZIN
632
hindrance to the SN2 reaction due to the steric reasons
and the electron-acceptor effect of two vicinal
N(O)=NOR groups, and the olefin formation was
impossible because of the lack of β-H-atoms.
(20 mmol) of 2,6-lutidine in 5 mL of anhydrous
acetonitrile was added at stirring 1.72 g (15 mmol) of
methanesulfonyl chloride. The reaction mixture self-
heated, compound I dissolved, and gradually crystals of
compound IVа started to precipitate. The reaction
mixture was stirred for 1 h at room temperature, and at
~0°С it was diluted with water (10 mL), the precipitate
was washed with ice water, dried, and recrystallized
from 10 mL of a mixture DMF–methanol, 1 : 1 v/v. Yield
1.79 g (94%), colorless crystals, mp 200.0–200.8°С
Sulfonates IVa–IVd and Va–Vd are quite stable
colorless crystalline substances; however, the decom-
position temperature of triflates IVb and Vb is by
~80°С lower than that of sulfonates IVа, IVc–IVd,
and Vа.
1
The composition and structure of sulfonates IVa–
IVd and Va–Vd was established from the data of the
(decomp.), t.decomp. 200–205°С. H NMR spectrum
(DMSO-d6), δ, ppm: 3.35 s (6H, CH3S, overlapped with
water signal), 4.16 s (6H, CH3O), 5.07 s (4H, SO3CH2).
13C NMR spectrum (DMSO-d6), δ, ppm: 37.20 (CH3S),
62.93 (CH3O), 63.23 (SO3CH2), 96.24 (СN2). Found, %:
C 22.39; H 4.19; N 14.70; S 16.70. C7H16N4O10S2.
Calculated, %: C 22.11; H 4.24; N 14.73; S 16.86.
1
elemental analysis and the H, 13C, and 19F NMR
spectra. The NMR spectra of all compounds are fully
consistent with the assumed structure. The electron-
acceptor effect of the triflate substituents in molecules
IVb and Vb results in the downfield shift of the 13C
NMR signals compared with the spectra of the other
sulfonates (from 0.5–0.7 ppm for the most remote
groups CH3O and CH3CH2O to 4.3–4.5 ppm for the
contiguous SO3CH2 group). The broadening of the
signal of the central carbon atom caused by the
quadrupole effect of the neighboring 14N nuclei [21–
23] was practically insignificant in the spectra of
compounds IVa–IVd and Va–Vd and reached
10–20% compared with the other signals.
2,2-Bis(ethoxy-NNO-azoxy)propane-1,3-diol bis-
methanesulfonate (Vа). To a slurry of 1.26 g (5 mmol)
of compound II in a solution of 2.14 g (20 mmol) of
2,6-lutidine in 7 mL of anhydrous acetonitrile was
added at stirring 1.49 g (13 mmol) of methanesulfonyl
chloride. The reaction mixture self-heated, compound
II dissolved. The reaction mixture was stirred for 1 h
at room temperature, diluted with water (20 mL), and
extracted with chloroform (3 × 10 mL) (TLC monitoring,
eluent benzene–ethyl acetate, 2 : 1, Rf 0.56). The extract
was washed with 5% HCl and with brine, filtered
through a short column packed with silica gel (5 g), the
solvent was distilled off in a vacuum. The residue was
crystallized by triturating with ethyl ether and
recrystallized from 10 mL of a mixture CH2Cl2–Et2O,
1 : 10 v/v, at ~0°C. Yield 1.99 g (97%), colorless
crystals, mp 101.8–102.3°С, t.decomp. 175–183°С. 1H
NMR spectrum, δ, ppm: 1.436 t (6H, CH3CH2O, J
7.2 Hz), 3.096 s (6H, CH3S), 4.497 q (4H, CH3CH2O,
EXPERIMENTAL
13
19
1H, C, and F NMR spectra were registered from
5% solution of compounds in CDCl3 (if not specially
indicated) on a spectrometer Avance III 500 Bruker
BioSpin (500.20, 125.78, and 470.66 MHz respect-
1
13
19
tively), internal reference for H and C TMS, for F,
CFCl3. Elemental analyses were carried out on an
analyzer vario MICRO cube. Melting points were
measured in open capillaries at the heating rate
~0.5 deg/min, for compound IVa, 1.2 deg/min. The
decomposition temperature (t.decomp.) after melting
was fixed at two points: the appearance of first gas
bubbles in the melt and rising of the melt column in the
capillary by 12 mm. The qualitative TLC analysis was
performed on Silufol UV-254 plates, development
under UV irradiation. Commercially available reagents
were used without additional purification. 2,2-Bis-
(methoxy-NNO-azoxy)-propane-1,3-diol (I) [12–14]
and 2,2-bis(ethoxy-NNO-azoxy)propane-1,3-diol (II)
[12, 19] were prepared by known procedures.
1
J 7.2 Hz), 5.109 s (4H, SO3CH2). H NMR spectrum
(300 MHz, DMSO-d6), δ, ppm: 1.31 t (6H, CH3CH2O),
3.31 s (6H, CH3S), 4.45 q (4H, CH3CH2O), 5.05 s (4H,
SO3CH2). 13C NMR spectrum, δ, ppm: 14.31
(CH3CH2O), 37.78 (CH3S), 63.12 (SO3CH2), 72.23
(CH3CH2O), 96.06 (CN2). 13C NMR spectrum (75 MHz,
DMSO-d6), δ, ppm: 14.35 (CH3CH2O), 37.38 (CH3S),
63.49 (SO3CH2), 71.96 (CH3CH2O), 96.49 (CN2).
Found, %: C 26.57; H 4.89; N 13.71; S 15.80.
C9H20N4O10S2. Calculated, %: C 26.47; H 4.94; N
13.72; S 15.70.
2,2-Bis(methoxy-NNO-azoxy)propane-1,3-diol-
bismethanesulfonate (IVа). To a slurry of 1.12 g
(5 mmol) of compound I in a solution of 2.14 g
2,2-Bis(methoxy-NNO-azoxy)propane-1,3-diol-
bistrifluoromethanesulfonate (IVb). To a slurry of
2.24 g (0.01 mol) of compound I in a solution of 3.39 g
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2,2-BIS(METHOXY- AND ETHOXY-NNO-AZOXY)PROPANE-...
633
(0.031 mol) 2,6-lutidine in 5 mL of anhydrous
acetonitrile was added at vigorous stirring and cooling
off in a vacuum. The residue was recrystallized from
methanol (25 mL) at ~0°C. Yield 3.56 g (71%),
colorless crystals, mp 126.3–126.8°С, t.decomp. 172–
with an ice bath 7.3
g
(0.026 mol) of
1
trifluoromethanesulfonic anhydride. The reaction mix-
ture self-heated, compound I dissolved. The reaction
mixture was stirred for 1 h at room temperature,
diluted with water (30 mL), and extracted with
chloroform (3 × 15 mL). The extract was washed with
5% HCl and with brine. The colored solution was
filtered through a short column packed with silica gel
(5 g), the solvent was distilled off in a vacuum. The
residue was recrystallized from ethanol (8 mL) at
cooling (–18°C). Yield 2.83 g (58%), colorless
crystals, mp 102.0–102.4°С, t.decomp. 102–106°С. 1H
NMR spectrum, δ, ppm: 4.232 s (6H, CH3O), 5.367 s
(4H, SO3CH2). 13C NMR spectrum, δ, ppm: 63.30
(CH3O), 67.52 (SO3CH2), 95.05 (CN2), 118.54 q
181°С. H NMR spectrum, δ, ppm: 4.097 s (6H,
CH3O), 4.882 s (4H, SO3CH2), 7.596 split t (4H, H3 , 5
,
P h
J 7.8, ~1.2 Hz), 7.717 t.t (2H, H4 , J 7.5, 1.2 Hz),
Ph
1
7.882 split d (4H, H2 , 6, J 7.3, ~1.2 Hz). H NMR
P h
spectrum (DMSO-d6), δ, ppm: 4.08 s (6H, CH3O), 4.85
(4H, SO3CH2), 7.71 br.t (4H, H3 , 5, J 7.7 Hz), 7.85 br.t
P h
(2H, H4 , J 7.4 Hz), 7.89 br.d (2H, H2 , 6, J 8.1 Hz).
Ph
P h
13C NMR spectrum, δ, ppm: 62.79 (CH3O), 63.24
(SO3CH2), 96.13 (CN2), 128.05, 129.63, 134.52,
134.69. Found, %: C 40.50; H 4.03; N 11.15; S 12.19.
C17H20N4O10S2. Calculated, %: C 40.47; H 4.00; N
11.11; S 12.71.
2,2-Bis(ethoxy-NNO-azoxy)propane-1,3-diol bis-
benzenesulfonate (Vc). To a mixture of 252 mg
(1 mmol) of compound II, 371 mg (2.1 mmol) of
benzenesulfonyl chloride, and 2 mL of anhydrous
acetonitrile was added at stirring 0.29 g (2.87 mmol) of
triethylamine. The reaction mixture self-heated,
compound II dissolved. The reaction mixture was
stirred for 1 h at room temperature, diluted with water
(5 mL), and extracted with chloroform (3× 5 mL). The
extract was filtered through a short column packed
with silica gel (3 g), the solvent was distilled off in a
vacuum. The residue was recrystallized from ethanol
(1.5 mL) at cooling (–18°C). Yield 450 mg (84%),
colorless crystals, mp 109.8–110.3°С. 1H NMR
spectrum, δ, ppm: 1.352 t (6H, CH3CH2O, J 7.2 Hz),
4.371 q (4H, CH3CH2O, J 7.2, JCH 148.2 Hz), 4.891 s
(4H, SO3CH2, JCH 160.2 Hz), 7.590 distorted t (4H,
1
(CF3S, JCF –319.9 Hz). 19F NMR spectrum, δ, ppm:
–74.186 s (CF3S). Found, %: C 17.89; H 2.40; S 12.64.
C7H10F6N4O10S2. Calculated, %: C 17.22; H 2.06; S
13.13.
2,2-Bis(ethoxy-NNO-azoxy)propane-1,3-diol bis-
trifluoromethanesulfonate (Vb) was similarly
obtained from 1.25 g (0.005 mol) of compound II. The
residue after distilling off the solvent was boiled with
hexane (3 × 5 mL), the hexane solution was decanted,
compound Vb crystallized from combined hexane
solutions on cooling (–18°C). Yield 2.00 g (77%),
colorless crystals, mp 57.8–58.5°С, t.decomp. 95–102°С.
1H NMR spectrum, δ, ppm: 1.442 t (6H, CH3CH2O, J
7.1 Hz), 4.511 q (4H, CH3CH2O, J 7.1 Hz), 5.366 s
(4H, SO3CH2). 13C NMR spectrum, δ, ppm: 14.26
(CH3CH2O), 67.65 (SO3CH2), 72.71 (CH3CH2O),
H
3 , 5, J 8 Hz), 7.725 distorted t (2H, H4 , J 7 Hz),
P h Ph
1
95.03 (CN2), 118.54 q (CF3S, JCF –319.9 Hz). 19F
7.882 distorted d (4H, H2 , 6, J 8 Hz). 13C NMR
P h
NMR spectrum, δ, ppm: –74.222 s (CF3S). Found, %:
C 21.30; H 2.53; S 12.55. C9H14F6N4O10S2. Calculated,
%: C 20.94; H 2.73; S 12.42.
spectrum, δ, ppm: 14.26 (CH3CH2O), 63.32 (SO3CH2),
71.95 (CH3CH2O), 96.11 (CN2), 128.02 (С2 , 6),
P h
129.59 (С3 , 5), 134.59 (C1 ), 134.64 (C4 ). Found,
P h
Ph
Ph
%: C 42.94; H 4.76; N 10.27. C19H24N4O10S2.
Calculated, %: C 42.85; H 4.54; N 10.52.
2,2-Bis(methoxy-NNO-azoxy)propane-1,3-diol
bisbenzenesulfonate (IVc). To a slurry of 2.24 g
(0.01 mol) of compound I in a solution of 3.39 g
(0.031 mol) of 2,6-lutidine in 5 mL of anhydrous
acetonitrile was added at vigorous stirring and cooling
with an ice bath 7.3 g (0.026 mol) of benzenesulfonyl
chloride. The reaction mixture self-heated, compound I
dissolved. The reaction mixture was stirred for 1 h at
room temperature, diluted with water (30 mL), and
extracted with chloroform (3 × 15 mL) (TLC monitor-
ring, eluent benzene–ethyl acetate, 5 : 1, Rf 0.43). The
extract was washed with 5% HCl and with brine. The
colored solution was filtered through a short column
packed with silica gel (5 g), the solvent was distilled
2,2-Bis(methoxy-NNO-azoxy)-propane-1,3-diol
bistosylate (IVd). To a mixture of 1.12 g (5 mmol) of
compound I, 2.14 g (11.2 mmol) of toluenesulfonyl
chloride, and 5 mL of anhydrous acetonitrile was
added at stirring 1.8 mL (12.9 mmol) of triethylamine.
The reaction mixture self-heated, compound II
dissolved, triethylamine hydrochloride precipitated.
The reaction mixture was stirred for 1 h at room
temperature, diluted with water (20 mL), and extracted
with chloroform (3 × 15 mL) (TLC monitoring, eluent
benzene–ethyl acetate, 3 : 1, Rf 0.56). The extract was
filtered through a short column packed with silica gel
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ZYUZIN
634
3. Yandovskii, V.N., Gidaspov, B.V., and Tselinskii, I.V.,
Russ. Chem. Rev., 1980, vol. 49, p. 237.
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1993, vol. 62, p. 143.
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vol. 102, p. 1135.
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(5 g), the solvent was distilled off in a vacuum. The
residue (2.35 g) was recrystallized in succession from
methanol (3 mL) and ethanol (6 mL) at cooling (–18°C).
Yield 1.75 g (66%), colorless crystals, mp 124.0–
1
124.4°С, t.decomp. 173–180°С. H NMR spectrum, δ,
ppm: 2.463 s (6H, CH3Ar, JCH 127.7 Hz), 4.101 s (4H,
CH3O, JCH 127.9 Hz), 4.831 s (4H, SO3CH2, JCH
160.0 Hz), 7.382 distorted d (4H, H3 , 5, J 8 Hz), 7.754
T s
distorted d (4H, H2 , 6, J 8 Hz). 13C NMR spectrum, δ,
T s
ppm: 21.75 (CH3Ar), 62.76 (CH3O), 63.07 (SO3CH2),
96.18 (CN2), 128.09 (С2 , 6), 130.24 (С3 , 5), 131.35
T s
T s
(C1 ), 145.97 (C4 ). Found, %: C 43.16; H 4.82; N
Ts
Ts
10.80. C19H24N4O10S2. Calculated, %: C 42.85; H 4.54;
N 10.52.
10. Yandovskii, V.N., Dobrodumova, E.Yu., and Tselin-
2,2-Bis(ethoxy-NNO-azoxy)propane-1,3-diol
bistosylate (Vd) was obtained from 252 mg (1 mmol)
of compound II similarly to compound IVd, TLC
monitoring, eluent benzene–ethyl acetate, 5 : 1, Rf 0.53.
The residue after distilling off solvent (2.35 g) was
recrystallized in succession from 1 mL of a mixture
methanol–water, 1 : 1 v/v, and 1 mL of ethanol at
cooling (–18°C). Yield 325 mg (58%), colorless
skii, I.V., Zh. Org. Khim., 1980, vol. 16, p. 933.
11. Zyuzin, I.N., Russ. Chem. Bull., 1985, vol. 34, p. 2433.
12. Marchenko, G.A., Mukhametzyanov, A.S., and
Tselinskii, I.V., J. Org. Chem. USSR (Engl. Transl.),
1985, vol. 21, p. 1297.
13. Zyuzin, I.N., Golovina, N.I., Lempert, D.B.,
Nechiporenko, G.N., and Shilov, G.V., Russ. Chem.
Bull., 2008, vol. 57, p. 632.
14. Zyuzin, I.N., Golovina, N.I., Lempert, D.B.,
and Shilov, G.V., Russ. Chem. Bull., 2010, vol. 59,
p. 1925.
1
crystals, mp 117.0–117.4°С. H NMR spectrum, δ,
ppm: 1.357 t (6H, CH3CH2O, J 7.2 Hz), 2.461 s (6H,
CH3Ar, JCH 127.5 Hz), 4.375 q (4H, CH3CH2O, J
7.2 Hz), 4.842 s (4H, SO3CH2, JCH 160.0 Hz), 7.377
15. Zyuzin, I.N., Russ. J. Appl. Chem., 2009, vol. 82,
distorted d (4H, H3 , 5, J 8 Hz), 7.752 distorted d (4H,
p. 1799.
T s
H2 , 6, J 8 Hz). 13C NMR spectrum, δ, ppm: 14.25
T s
16. Zyuzin, I.N. and Lempert, D.B., Russ. Chem. Bull.,
(CH3CH2O), 21.75 (CH3Ar), 63.18 (SO3CH2), 71.91
2009, vol. 58, p. 2173.
17. Zyuzin, I.N., Suponitsk, K.Yu., and Sheremetev, A.B.,
(CH3CH2O), 96.18 (CN2), 128.07 (С2 , 6), 130.21
T s
(С3 , 5), 131.46 (C1 ), 145.89 (C4 ). Found, %: C
J. Heterocycl. Chem., 2012, vol. 49, p. 561.
T s
Ts
Ts
45.15; H 5.51; N 10.30. C21H28N4O10S2. Calculated, %:
C 42.85; H 4.54; N 10.52.
18. Marchenko, G.A., Mukhametzyanov, A.S., Tselin-
skii, I.V., and Ermoshkin, I.V., J. Org. Chem. USSR
(Engl. Transl.), 1985, vol. 21, p. 1300.
ACKNOWLEDGMENTS
19. Zyuzin, I.N., Golovina, N.I., and Shilov, G.V., Russ. J.
Org. Chem., 2010, vol. 46, p. 1085.
The author is grateful to PhD A.V. Chernyak for
registering the NMR spectra.
20. Jones, D.N., Comprehensive Organic Chemistry, Bar-
ton, D. and Ollis, W.D., Eds., Oxford: Pergamon, Press,
1979, vol. 3, 1338 p.
21. Redkin, Yu.A., Marchenko, G.A., Punegova, L.N.,
Stepanov, G.S., and Tselinskii, I.V., Russ. J. Org.
Chem. USSR (Engl. Transl.), 1988, vol. 24, p. 441.
22. Zyuzin, I.N., Russ. J. Org. Chem., 2013, vol. 49, p. 536.
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