[(Polyfluoroalkoxy)methyl]thiiranes and 2-anilinoethanethiols

Article abstract of DOI:10.1134/S1070428008070026

By reaction of appropriate oxiranes with thiourea [(polyfluoroalkoxy) methyl]-substituted thiiranes were obtained that are key compounds for the synthesis of perfluoro-containing 1,2-aminopropanethiols.

Full text of DOI:10.1134/S1070428008070026

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 7, pp. 946−949. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © A.T. Guseinova, A.M. Magerramov, M.A. Allakhverdiev, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 7,
pp. 958−961.
[(Polyfluoroalkoxy)methyl]thiiranes and 2-Anilinoethanethiols
A. T. Guseinova, A. M. Magerramov, and M. A. Allakhverdiev
Baku State University, Baku, AZ-1148 Azerbaidzhan
e-mail: rector@bsu.az
Received July 24, 2007
Abstract—By reaction of appropriate oxiranes with thiourea [(polyfluoroalkoxy)methyl]-substituted thiiranes
were obtained that are key compounds for the synthesis of perfluoro-containing 1,2-aminopropanethiols.
DOI: 10.1134/S1070428008070026
Ia_Id + NaOH
Many thiiranes attract a special attention of
researchers as valuable initial synthons for the synthesis
of versatile physiologically active substances, antidotes
of heavy metals, radioprotectors, psychotropic and neuro-
tropic compounds, pharmaceuticals used in the therapy
of cancer in combination with alkylating antitumor prep-
arations. They are also employed as monomers in produc-
tion of specialty rubbers, as regulators of polymerization
processes, antioxidants, and for other purposes [1–3].
ROCH2CH
CH2
O
IIa_IId
We formerly established [2–7] that anionotropic
substitution of the oxygen atom in oxiranes by sulfur in
the presence of sulfuric acid resulted in increased yields
of alkoxy-substituted thiiranes. However the attempt to
synthesize polyfluoroalkyl-substituted thiiranes by this
procedure was unsuccessful. The reaction led
predominantly to the formation of the side polymeric
product decreasing the yield of the target compound.
In this connection the synthesis of new representatives
of perfluoro-containing thiiranes, their amino derivatives,
and the study of their functional properties is an urgent
problem.
Therefore we synthesized polyfluoroalkyl-containing
thiiranes IIIa–IIId by the reaction of the corresponding
oxiranes IIa–IId with thiourea in methanol solution.
The key compounds for the preparation of [(poly-
fluoroalkoxy)methyl]fluoro-substituted oxiranes served
polyfluoro-containing chlorohydrins Ia–Id obtained by
reaction of 1,2-epoxy-3-chloropropane with various
polyfluoro-containing aliphatic alcohols in the presence
of sodium.
CH3OH
_(NH2)2CO
IIa_IId + (NH2)2CS
ROCH2CH
CH2
S
IIIa_IIId
In the second stage by reaction of chlorohydrins Ia–
Id with alkali oxiranes IIa–IId were synthesized. The
latter are synthons for preparation of the thiiranes in
question.
In order to study the effect of the polyfluoroalkyl
moiety on the antioxidant and antimicrobial activity of
1,2-aminopropanethiols we carried out reactions of
thiiranes IIIa–IIId with aniline.
ROH + CH2
CHCH2Cl
ROCH2CHCH2Cl
O
OH
Ia_Id
IIIa_IIId + H2NC6H5
ROCH2CHCH2NHC6H5
R = CF3CH2 (a), C2F5CH2 (b), C3F7CH2 (c),
CHF2CF2CH2 (d).
SH
IVa_IVd
The reaction was carried out in the presence of a fine
powder of potassium or sodium hydroxide in ether or by
treating with 20% solution of these alkali.
The synthesized [(polyfluoroalkoxy)methyl]-sub-
stituted thiiranes and 1,2-aminopropanethiols are color-
946

[(POLYFLUOROALKOXY)METHYL]THIIRANES AND 2-ANILINOETHANETHIOLS
947
EXPERIMENTAL
less fluids with a specific odor. 1,2-Aminopropanethiols
get yellow at prolonged storage.
1H NMR spectra were registered on a spectrometer
BrukerAM-300 at operating frequency 300 MHz, solvent
CDCl3, internal reference TMS. IR spectra were recorded
on a spectrophotometer UR-20. The purity of reaction
products was checked by TLC on Silufol UV-254 plates.
The purity of compounds obtained was checked by
elemental analysis, TLC, and GLC, and their structure
was proved by IR and 1H NMR spectroscopy.
In the IR spectra of perfluoro-containing thiiranes
IIIa–IIId a strong absorption band is present in the region
640–660 cm–1 characteristic of the three-membered
thiirane ring, and in the regions 1110–1130 and 160–
1375 cm–1 appear absorption bands of the stretching
vibrations of C–F bond.
3-(2,2,2-Trifluoroethoxy)-1-chloropropan-2-ol
(Ia). To a cooled mixture of 10 g (0.1 mol) of 2,2,2-tri-
fluoroethanol, 2.3 g (0.1 g-atom) of sodium, and 9.25 g
(0.1 mol) of 1,2-epoxy-3-chloropropane was added at
vigorous stirring a solution of 8 g of NaOH in 30 ml of
H2O, and the mixture was left standing at room
temperature for 10 h. Then the organic layer was
separated, washed twice with water, and dried with
Na2SO4. The reaction product was subjected to vacuum
distillation. Yield 9.6 g, bp 86–87°C (20 mm Hg), nD20
1.3971, d240 1.3791. MRD 33.67, calc. 33.33. IR spectrum,
The IR spectra of polyfluoroalkyl-containing 1,2-amino-
propanethiols IVa–IVd in contrast to initial thiiranes
IIIa–IIId lack the absorption band characteristic of the
thiirane ring in the region 640–660 cm–1, but contain the
characteristic absorption band in the region 3340–
3360 cm–1 corresponding to the stretching vibrations of
NH bonds of secondary amino groups. The stretching
vibrations of SH bond give rise to a weak band in the
region 2540–2545 cm–1. Alongside the above bands all
spectra contain strong absorption bands in the regions
1445–1460, 1500–1510, and 1590–1610 cm–1 character-
istic of the stretching vibrations of the C=C bonds in
benzene ring.
1
ν, cm–1: 3155–3250 (OH), 675 (C–Cl). H NMR
spectrum, δ, ppm: 3.21 m (2H, OCH2), 3.74 m (1H, CH),
3.57 m (2H, CH2Cl). Found, %: C 31.03; H 4.02; Cl 18.27.
C5H8ClF3O2. Calculated, %: C 31.17; H 4.15; Cl 18.44.
Compounds Ib–Id were similarly obtained.
3-(3,3,3,2,2-Pentafluoropropoxy)-1-chloropropan-
2-ol (Ib) was obtained from 15 g (0.1 mol) of 3,3,3,2,2-
pentafluoropropanol and 9.25 g (0.1 mol) of 1,2-epoxy-
3-chloropropane. Yield 13.8 g (57%), bp 87°C (22 mm
Hg), nD20 1.3823. IR spectrum, ν, cm–1: 3165–3230 (OH),
670 (C–Cl). 1H NMR spectrum, δ, ppm: 3.25 m (2H,
OCH2), 3.69 m (1H, CH), 3.60 m (2H, OCH2). Found,
%: C 29.53; H 3.14; Cl 14.48. C6H8ClF5O2. Calculated,
%: C 29.69; H 3.29; Cl 14.64.
1
In the H NMR spectrum of compound IIId two
protons of the methylene group of thiirane ring appear
in the strong field as two doublets at δ 2.1 and 2.4 ppm
corresponding to cis- and trans-positions of hydrogen
atoms. The signal of methine proton due to coupling with
the protons of two adjacent methylene groups appears at
2.9 ppm as a quintet. The protons of two methylene
groups linked to oxygen (CH2OCH2) give rise to a multi-
plet at 3.8 ppm. The signal from the proton of CHF2
3-(4,4,4,3,3,2,2-Heptafluorobutoxy)-1-chloro-
propan-2-ol (Ic) was obtained from 20 g (0.1 mol) of
4,4,4,3,3,2,2-heptafluorobutanol and 9.25 g (0.1 mol) of
1,2-epoxy-3-chloropropane. Yield 17.5 g (60%), bp 91°C
(15 mm Hg), nD20 1.3739. IR spectrum, ν, cm–1: 3170–
1
fragment appears downfield at 5.9 ppm. The H NMR
spectra of the other perfluoro-containing thiiranes have
similar patterns.
1H NMR spectra of perfluoroalkyl-containing
1,2-aminopropanethiols IVa–IVd resemble the spectra
of the corresponding thiiranes but the signals of protons
of SH and NH groups and also of three protons of the
CHCH2 fragment are observed in all the spectra as
multiplets in the 2.9–3.7 ppm, and nonequivalent protons
of the benzene ring give rise to a multiplet in the region
6.0–7.2 ppm.
1
3225 (OH), 635 (C–Cl). H NMR spectrum, δ, ppm:
3.35 m (2H, OCH2), 3.75 m (1H, CH), 3.67 m (2H,
CH2Cl). Found, %: C 28.61; H 2.59; Cl 11.98.
C7H8ClF7O2. Calculated, %: C 28.72; H 2.74; Cl 12.14.
3-(3,3,2,2-Tetrafluoropropoxy)-1-chloropropan-2-
ol (Id) was obtained from 13.2 g (0.1 mol) of 3,3,2,2-
tetrafluoropropanol and 9.25 g (0.1 mol) of 1.2-epoxy-
3-chloropropane. Yield 9.7 g (60%), bp 80–82°C (15 mm
Hg), nD20 1.3875. IR spectrum, ν, cm–1: 3145–3220 (OH),
638 (C–Cl). 1H NMR spectrum, δ, ppm: 3.28 m (2H,
OCH2), 3.80 m (1H, CH), 3.60 m (2H, CH2Cl). Found,
It was shown by special investigation that the syn-
thesized perfluoro-containing thiiranes possess high
antiwelding properties, and their amino derivatives
exhibit antimicrobial activity in lubricants.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008

GUSEINOVA et al.
948
solvent the reaction product was subjected to vacuum
distillation. Yield 11 g (63%), bp 80°C (18 mm Hg), nD20
1.4083. IR spectrum, ν, cm–1: 645 (thiirane), 1115, 1365
(C–F). 1H NMR spectrum, δ, ppm: 2.15, 2.30 d (2H,
cis- and trans-CCH2), 2.90 q (1H, CH), 3.8 m (4H,
CH2OCH2). Found %; C 34.72; H 3.91; S 18.45.
C5H7F3OS. Calculated, %: C 34.88; H 4.07; S 18.60.
%: C 31.95; H 3.83; Cl 15.63. C6H9ClF4O2. Calculated,
%: C 32.07; H 4.01; Cl 15.81.
2-[(2,2,2-Trifluoroethoxy)methyl]oxirane (IIa). To
a solution of 19.25 g (0.1 mol) of 3-(2,2,2-trifluoro-
ethoxy)-1-chloropropan-2-ol (Ia) in 50 ml of anhydrous
ether at vigorous stirring was added by portions 11.2 g
(0.2 mol) of powdered potassium hydroxide. Therewith
the reaction mixture strongly heated. Then it was heated
to 60°C for 1.5 h. On cooling the ether layer was
separated, the residue was extracted with anhydrous ether
(3×30 ml). The ether was distilled off, the reaction
product was distilled at ordinary pressure. Yield 9.36 g
(60%), bp 132–135°C, d240 1.2669, nD20 1.3581. MRD
26.93, calc. 26.62. IR spectrum, ν, cm–1: 829, 880, 910,
Compounds IIIb–IIId were similarly obtained.
2-[(3,3,3,2,2-Pentafluoropropoxy)methyl]thiirane
(IIIb) was obtained from 20.6 g (0.1 mol) of oxirane IIb
and 7.6 g (0.1 mol) of thiourea. Yield 12 g (57%), bp
100°C (50 mm Hg), nD20 1.3967. IR spectrum, ν, cm–1:
1
650 (thiirane), 1118, 1350 (C–F). H NMR spectrum, δ,
ppm: 2.10, 2.35 d (2H, cis- and trans-CCH2), 2.85 q (1H,
CH), 3.85 m (4H, H2COCH2). Found, %: C 32.26; H
3.02; S 14.25. C6H7F5OS. Calculated, %: C 32.43; H
3.15; S 14.41.
1
1220, 1285 (oxirane). H NMR spectrum, δ, ppm: 2.65 m
(2H, CH2O), 3.35 m (3H, CH, CH2O). Found, %: C 38.32;
H 4.36. C5H7F3O2. Calculated, %: C 38.46; H 4.49.
Compounds IIb–IId were similarly obtained.
2-[(4,4,4,3,3,2,2-Heptafluorobutoxy)methyl]-
thiirane (IIIc) was obtained from 25.6 g (0.1 mol) of
oxirane IIc and 7.6 g (0.1 mol) of thiourea. Yield 13 g
(49%), bp 98°C (50 mm Hg), nD20 1.3879. IR spectrum,
ν, cm–1: 655 (thiirane), 1120, 1365 (C–F). 1H NMR spec-
trum, δ, ppm: 2.15, 2.30 d (2H, cis- and trans-CCH2),
2.90 q (1H, CH), 3.80 m (4H, H2COCH2). Found, %:
C 30.71; H 2.41; S 11.59. C7H7F7OS. Calculated, %:
C 30.88; H 2.57; S 11.76.
2-[(3,3,3,2,2-Pentafluoropropoxy)methyl]oxirane
(IIb) was obtained from 24.3 g (0.1 mol) of compound
Ib and 11.2 g (0.2 mol) of potassium hydroxide. Yield
16 g (52%), bp 80–81°C (83 mm Hg), nD20 1.3419. IR
spectrum, ν, cm–1: 817, 875, 915, 1280 (oxirane). 1H NMR
spectrum, δ, ppm: 2.55 m (2H, CH2O), 3.25 m (3H, CH,
CH2O). Found, %: C 34.78; H 3.25. C6H7F5O2.
Calculated, %: C 34.95; H 3.40.
2-[(4,4,4,3,3,3,2,2-Heptafluorobutoxy)methyl]-
oxirane (IIc) was obtained from 29.2 g (0.1 mol) of
compound Ic and 11.2 g (0.2 mol) of potassium
hydroxide. Yield 11 g (43%), bp 79°C (50 mm Hg), nD20
1.3352. IR spectrum, ν, cm–1: 825, 880, 919, 1215, 1275
(oxirane). 1H NMR spectrum, δ, ppm: 2.60 m (2H,
CH2O), 3.35 m (3H, CH, CH2O). Found, %: C 32.68; H
2.58. C7H7F7O2. Calculated, %: C 32.80; H 2.73.
2-[(3,3,2,2-Tetrafluoropropoxy)methyl]thiirane
(IIId) was obtained from 18.7 g (0.1 mol) of oxirane IId
and 7.6 g (0.1 mol) of thiourea. Yield 8.5 g (42%), bp
79–80°C (3 mm Hg), nD20 1.4120. IR spectrum, ν, cm–1:
645 (thiirane), 1130, 1370 (C–F). 1H NMR spectrum, δ,
ppm: 2.10, 2.25 d (2H, cis- and trans-CCH2), 2.85 q (1H,
CH), 3.85 m (4H, H2COCH2), 5.90 (1H, CHF2). Found,
%: C 35.11; H 3.78; S 15.56. C6H8F4OS. Calculated, %:
C 35.29; H 3.92; S 15.69.
2-[(3,3,2,2-Tetrafluoropropoxy)methyl]oxirane
(IId) was obtained from 22.5 g (0.1 mol) of compound
Id and 11.2 g (0.2 mol) of potassium hydroxide. Yield
19 g (48%), bp 79–80°C (90 mm Hg), nD20 1.3568. IR
spectrum, ν, cm–1: 820, 885, 915, 1220, 1278 (oxirane).
1H NMR spectrum, δ, ppm: 2.75 m (2H, CH2O), 3.55 m
(3H, CH, CH2O), 5.9 m (1H, CHF2). Found, %: C 38.13;
H 4.11. C6H8F4O2. Calculated, %: C 38.30; H 4.26.
1-Anilino-3-(2,2,2-trifluoroethoxy)propane-2-thiol
(IVa). Into a glass ampule of 50 ml capacity was charged
17.2 g (0.1 mol) of thiirane and 18.6 g (0.2 mol) of aniline.
The ampule was sealed and heated for 10 h at 95–100°C.
On cooling the ampule was opened, excess aniline and
unreacted thiirane was distilled off, and the residue was
subjected to vacuum distillation. Yield 19 g (72%), bp
122°C (0.3 mm Hg), nD20 1.4975. IR spectrum, ν, cm–1:
2-[(2,2,2-Trifluoroethoxy)methyl]thiirane (IIIa). A
mixture of 8.6 g (0.1 mol) of thiourea, 15.6 g (0.1 mol)
of compound IIa, and 30 ml of methanol was stirred for
2 h at 50°C, then it was cooled, washed with water,
extracted with tetrachloromethane, and dried with
anhydrous magnesium sulfate. On distilling off the
1
1445, 1510, 1595 (C=C), 2450 (SH), 3350 (NH). H
NMR spectrum, δ, ppm: 2.90–3.50 m (7H, SH, NH,
CH2CHCH2), 6.1–7.1 m (5H, C6H5). Found %; C 52.43;
H 5.43; N 5.43; S 12.61. C11H14F3NOS. Calculated, %:
C 52.59; H 5.58; N 5.58; S 12.75.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008

[(POLYFLUOROALKOXY)METHYL]THIIRANES AND 2-ANILINOETHANETHIOLS
949
Thiols IVb–IVd were similarly obtained.
thiirane IIId and 18.6 g (0.02 mol) of aniline. Yield 18 g
(61%), bp 130°C (0.3 mm Hg), nD20 1.5010. IR spectrum,
ν, cm–1: 1455, 1515, 1590 (C=C), 2550 (SH), 3355 (NH).
1H NMR spectrum, δ, ppm: 2.85–3.45 m (7H, SH, NH,
CH2CHCH2), 6.20–7.35 m (5H, C6H5). Found, %:
C 48.32; H 4.92; N 4.56; S 10.61. C12H15F4NOS.
Calculated, %: C 48.48; H 5.05; N 4.71; S 10.77.
1-Anilino-3-(3,3,3,2,2-pentafluoropropoxy)-
propane-2-thiol (IVb) was obtained from 22.3 g (0.1 mol)
of thiirane IIIb and 18.6 g (0.02 mol) of aniline. Yield
18.6 g (59%), bp 122°C (0.3 mm Hg), nD20 1.4863. IR
spectrum, ν, cm–1: 1450, 1515, 1590 (C=C), 2550 (SH),
3355 (NH). 1H NMR spectrum, δ, ppm: 2.85–3.45 m
(7H, SH, NH, CH2CHCH2), 6.1–7.1 m (5H, C6H5).
Found, %: C 51.83; H 4.92; N 4.89; S 11.38.
C12H14F3NOS. Calculated, %: C 51.99; H 5.05; N 5.05;
S 11.55.
REFERENCES
1. Fokin, A.V., Allakhverdiev, M.A., and Kolomiets, A.F.,
Usp. Khim., 1990, vol. 58, p. 705.
1-Anilino-3-(4,4,4,3,3,2,2-heptafluorobutoxy)-
propane-2-thiol (IVc) was obtained from 27.2 g (0.1 mol)
of thiirane IIIc and 18.6 g (0.02 mol) of aniline. Yield
24 g (65%), bp 130°C (0.2 mm Hg), nD20 1.4775. IR
spectrum, ν, cm–1: 1470, 1520, 1585 (C=C), 2545 (SH),
3345 (NH). 1H NMR spectrum, δ, ppm: 2.90–3.40 m
(7H, SH, NH, CH2CHCH2), 6.15–7.15 m (5H, C6H5).
Found, %: C 42.58; H 3.71; N 38.23; S 8.61.
C13H14F7NOS. Calculated, %: C 42.74; H 3.84; N 38.36;
S 8.77.
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Azerb. Khim. Zh., 1991, p. 95.
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1-Anilino-3-(3,3,2,2-tetrafluoropropoxy)propane-
2-thiol (IVd) was obtained from 20.4 g (0.1 mol) of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008