Synthesis and structure of some aryl-substituted thiiranes

Article abstract of DOI:10.1023/A:1022558000694

A number of aryl-substituted 1,2-chlorohydrins was prepared by treating 1,2-epoxy-3-chloropropane with arylmagnesium bromide. The reaction of the aryl-substituted 1,2-chlorohydrins with sodium hydroxide solution furnished the corresponding oxiranes, the k

Full text of DOI:10.1023/A:1022558000694

Russian Journal of Organic Chemistry, Vol. 38, No. 11, 2002, pp. 1620 1623. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 11, 2002,
pp. 1676 1679.
Original Russian Text Copyright
2002 by Allakhverdiev, Mustafaev, Farzaliev.
Synthesis and Structure of Some Aryl-substituted Thiiranes
M. A. Allakhverdiev, K. N. Mustafaev, and V. M. Farzaliev
Baku State University, Baku, 670603 Azerbaidzhan
Additives Chemistry Institute, Kuliev Azerbaidzhan Academy of Sciences, Baku, 670603 Azerbaidzhan
Received May 6, 2002
Abstract A number of aryl-substituted 1,2-chlorohydrins was prepared by treating 1,2-epoxy-3-chloro-
propane with arylmagnesium bromide. The reaction of the aryl-substituted 1,2-chlorohydrins with sodium
hydroxide solution furnished the corresponding oxiranes, the key compounds in the synthesis of a number of
previously unknown thiiranes.
We report here on the studies concerning prepara-
tion of thiiranes and their amino derivatives [1 12].
1,2-chlorohydrin I IV with 28% solution of sodium
hydroxide.
To this end as initial products aryl-substituted
1,2-chlorohydrins I IV were synthesized from
Aryl-substituted thiiranes VIII XII were prepared
by thioepoxidation of the corresponding oxiranes
V VIII with thiourea in the presence of sulfuric acid.
1,2-epoxy-3-chloropropane
bromides.
and
arylmagnesium
We demonstrated that the acid catalysis (here with
sulfuric acid) plays an essential part in the aniono-
tropic conversion of oxiranes into thiiranes and it
ensures high yields of the target products (70 85%).
The structure of compounds I XII obtained was
confirmed by IR, 1H and 13C NMR spectra. The
physical constants of compounds I XII are listed in
Table 1.
The studies showed that the best yields of 1,2-
chlrohydrins I IV were obtained at the ratio of aryl-
magnesium bromide to 1,2-epoxy-3-chloropropane of
1: 2. At equimolar reagents ratio the yield of the
target product strongly decreased. We succeeded in
raising the yield of 1,2-chlorohydrins I IV by 20
30%, and also refined the data on certain physico-
chemical constants that had been previously not
enough precisely determined as was indicated in [13].
In the IR spectra of all 1,2-chlorohydrins I IV
synthesized is observed a broad absorption band in
1
the 3380 3400 cm region that is conserved at dilu-
tion with CCl4 to the concentration of 0.005 M. This
fact is incompatible with an intermolecular associa-
tion, and the band is characteristic of an intra-
molecular hydrogen bond O Cl [15].
We established that in all cases alongside
1.2-chlorohydrins I IV arose a small amount of a
side products, 1-chloro-3-bromo-2-propanol and
chlorocyclopropanol [14].
The stretching vibrations of the C Cl bond appear
1
in all IR spectra in the region 765 785 cm . In the
The synthesis of aryl-substituted oxiranes V VIII
was accomplished by reaction of an appropriate
IR spectra were also revealed weak absorption bands
1
in 2000 1720 cm region characterizing the substitu-
tion types in the aromatic ring [16]. In the IR spectra
of the obtained oxiranes V VIII in contrast to the
1,2-chlorohydrins are observed strong bands in the
1
region 830 840, 1015 1020, and 1240 1250 cm
1070-4280/02/3811-1620$27.00 2002 MAIK Nauka/Interperiodica

SYNTHESIS AND STRUCTURE OF SOME ARYL-SUBSTITUTED THIIRANES
1621
Table 1. Yields, melting points, and MRD values of compounds I XII
bp,
C
(mm Hg)
MRD
Found, %
H
Calculated, %
Compd. Yield,
no.
n2D0
d240
Formula
Rf
%
found
calcu-
lated
C
Cl
or S
C
H
Cl
or S
I
II
III
65 106 (1.3) 1.5410 1.1272 51.48 51.17 65.27 6.90 19.34 C10H13OCl 65.04 7.10 19.20 0.43
61 140 (2.8) 1.5285 1.0791 60.72 60.41 67.94 7.87 16.38 C12H17OCl 67.76 8.06 16.66 0.51
71 134 135 1.5398 1.1271 51.39 51.17 64.91 6.83 19.07 C10H13OCl 65.04 7.10 19.20 0.53
(4)
IV
56 145 146 1.6230 1.2532 61.89 61.89 70.67 5.82 16.35 C13H13OCl 70.35 5.94 16.07 0.62
(1.1)
V
68 70 (1.3) 1.5192 1.0155 44.31 44.20 80.81 8.29
C10H12O 81.04 8.16
C12H16O 81.77 9.15
C10H12O 81.04 8.16
0.68
0.86
0.77
VI
VII
63 98 (3)
1.5135 0.9854 53.84 54.16 81.52 9.36
1.5220 1.0266 44.03 44.20 81.17 8.03
74 90 91
(0.4)
VIII
85 154 155 1.6131 1.1430 56.07 56.04 84.42 6.29
(4)
C13H12O 84.75 6.57
0.41
IX
X
83 98 (1.3) 1.5642 1.0518 50.81 50.68 73.43 7.18 19.31 C10H12S
73.12 7.36 19.52 0.71
74.94 8.39 16.67 0.82
73.12 7.36 19.52 0.75
70 110 (2)
1.5430 1.0037 60.36 60.53 74.67 8.52 16.58 C12H16S
1.5625 1.0469 50.92 50.68 73.31 7.12 19.16 C10H12S
XI
71 129
(2.5)
XII
80 134 135 1.6508 1.1427 62.21 62.56 77.69 6.23 16.37 C13H12S
(1)
77.95 6.04 16.07 0.74
Table 2. Parameters of 1H NMR and IR spectra of compounds I XII
1
1H NMR spectrum (CCl4), , ppm
Compd.
IR spectrum, cm
no. CH3, s ArCH2, d
CH2X, d CH, m Ar, s OH CH2Cl
oxirane
thiirane frequencies of
substitution type
I
II
2.15
1.30
2.65
2.60
3.30
3.25
3.65
1.85
3.70
3.50
6.70 3400 770
6.75 3380 765
840, 1790, 1960
1790, 1910
III
IV
2.65
t
2.45
3.30
3.15
6.95 3390 765
840, 1790, 1960
830, 1720, 1930
4.15
6.65 3390 785
7.10
6.60
6.70
6.95
7.2
V
VI
VII
VIII
2.20
1.30
2.65
2.60
2.65
3.20
2.35 2.70 2.80
2.25 2.60 2.75
2.20 2.45 2.85
2.35 2.65 3.30
830, 1020, 1250
840, 1020, 1240
830, 1015, 1240
830, 1015, 1245
805, 1785, 1900
810, 1780, 1820
700, 730, 1810
815, 1720, 1925
8.2
IX
X
2.20
1.20
2.70
2.60
2.75
3.20
2.08 2.25 2.70
2.10 2.30 2.75
1.85 2.25 2.85
2.10 2.30 3.20
6.60
6.75
635
625
625
625
820, 1700, 1910
820, 1710, 1910
690, 750, 1930
805, 1780, 1910
XI
XII
6.85
7 8
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 11 2002

1622
ALLAKHVERDIEV et al.
corresponding to asymmetrical, symmetrical, and
pulse vibrations of the oxirane ring. Unlike the IR
spectra of oxiranes, in the spectra of thiiranes IX XII
are present absorption bands at 625 635 cm from
the stretching vibrations of the C S bond in the three-
membered thiirane ring.
compounds synthesized was checked by GLC using
chromatograph Tsvet-126 equipped with a flame-
ionization detector, glass column 1500 3 mm,
stationary phase 5% SE-30 on Chromaton N-AW,
carrier gas nitrogen. TLC of compounds I XII was
performed on Silufol UV-254 plates using as eluent
ethanol hexane mixture, 1: 5.
1
1
In the H NMR spectra of 1,2-chlorohydrins I IV
in the strong field at 1.30 2.15 ppm appear signals
of protons from methyl groups attached to aromatic
rings, and doublet signals in the region 2.60
2.65 ppm correspond to the methylene protons linked
to the benzene ring. The proton signals of the methyl-
ene group in compound III bonded to benzyl group
and the neighboring methine group appear at 1.5
1.9 ppm as a quartet due to spin-spin coupling. The
protons signals from the methylene groups linked to
chlorine in the molecules of 1,2-chlorohydrins give
rise to doublet in the 3.15 3.30 ppm region, and the
signal of methine proton appears as a multiplet at
3.50 4.15 ppm.
4-Phenyl-1-chloro-2-butanol (III). To an ethereal
solution of benzylmagnesium bromide obtained by a
common procedure from 0.5 mol (93 g) of benzyl
bromide, 0.5 g-atom (12 g) of magnesium in 200 ml
of dry ether in the presence of 2 3 iodine crystals
under external cooling with an ice bath was added
dropwise at stirring a solution of 1 mol (92.5 g) of
1,2-epoxy-3-chloropropane in 100 ml of dry ether.
Then the reaction mixture was heated to 35 C for 2 h
more at constant stirring. Then at cooling the flask
with an ice bath the reaction mixture was quenched
with 10% solution of hydrochloric acid till two
transparent layers formed. The upper organic layer
was separated, the water layer was thrice extracted
with ether. The combined organic solutions were
washed with water and dried with anhydrous sodium
sulfate. After removing the solvent the residue was
subjected to a vacuum distillation. We obtained
65.5 g of 4-phenyl-1-chloro-2-butanol (III). Yield of
compound III 71%, bp 134 135 C (4 mm Hg), nD20
1.5398, d240 1.1271. Published data [13]: bp 158
160 C (23 mm Hg), n2D0 1.5371.
A strong signal in the downfield part of the
1H NMR spectra (6.70 6.95 ppm) originates from
aromatic protons, and naphthyl protons of compound
IV give rise to a multiplet at 7.80 8.10 ppm. The
proton signal of the hydroxy group in all studied
1,2-chlorohydrins overlapped with the resonance of
CH2Cl group as was proved by recording the spec-
trum in the presence of D2O.
1
In the H NMR spectra of oxiranes V VIII the
Likewise by reaction of p-tolyl-, p-isopropyl-
protons of CH2 group in the oxirane ring give rise to
two doublets at 2.20 2.35 ppm and 2.45 2.70 ppm
which correspond to hydrogens located in cis- and
trans-positions. The methine proton signals in the
oxirane ring of compounds V VIII are shifted upfield
as compared with 1,2-chlorohydrins and appear at
phenyl-,
-naphthylmagnesium bromides with
1,2-epoxy-3-chloropropane in a dry ether solution
were prepared the corresponding 1,2-chlorohydrins
I, II, IV. Their physical constants are listed in
Table 1. 1-Chloro-3-(4-methylphenyl)-2-propanol (I)
and 1-chloro-3-( -naphthyl)-2-propanol (IV) were
prepared as described in [13]; as mentioned in [13],
the data on the constants of compounds I, IV were
incorrect.
1
2.70 3.30 ppm. The H NMR spectra of thiiranes
IX XII are similar in appearance to the oxirane
spectra, but the proton signals of the CH2 group in
the thiirane ring are shifted upfield and give two
doublets in the region 1.85 2.10 and 2.70 3.20 ppm.
1,2-epoxy-4-phenylbutane (VII). To a mixture of
18.5 g (0.1 mol) of 1-chloro-4-phenyl-2-butanol and
50 ml of hexane at vigorous stirring was added drop-
wise 20 g of 29% NaOH solution. Then the reaction
mixture was heated for 2 h to 60 C. On cooling the
reaction mixture was several times washed with water
till neutral washings and dried with anhydrous
sodium sulfate. On removing the solvent the reaction
product was subjected to vacuum distillation to obtain
11 g (24%) of compound VII, bp 90 91 C (0.4 mm
EXPERIMENTAL
1H NMR spectra were recorded on spectrometer
Varian T-60 at operating frequency 60 MHz from
solutions in CCl4 with TMS as internal reference.
13C NMR spectra were registered on Varian VXR-
400 instrument at operating frequency 100 MHz. IR
spectra were measured on spectrophotometer
Specord-75 IR from liquid films in the region 400
1
Hg), n2D0 1.5220; H NMR spectrum (CCl4), , ppm:
1
4000 cm (with prisms of KBr, NaCl, LiF). The
2.20, 2.45 (2H, CH2-oxirane), 2.85 (1H, CH), 2.65 t
(2H, ArCH2), 6.95 s (5H, C6H5); 13C NMR spectrum
progress of reactions was monitored and the purity of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 11 2002

SYNTHESIS AND STRUCTURE OF SOME ARYL-SUBSTITUTED THIIRANES
1623
(CDCl3), , ppm: 52.57 (CH), 38.49 (CH2-oxirane),
38.43 (CH2CH), 147.42 (Ci), 134.30 (Cp), 129.31
(Co), 127.54 (Cm). Found, %: C 81.17; H 8.03.
C10H8O. Calculated, %: 81.04; H 8.16.
3. Allakhverdiev, M.A., Farzaliev, V.M., Khalilo-
va, A.Z., and Sultanov, Yu.M., Zh. Org. Khim.,
1986, vol. 22, no. 1, pp. 90 93.
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va, A.Z., Ibragimov, N.Yu., Sultanov, Yu.M., and
Cherkasova, E.M., Zh. Org. Khim., 1986, vol. 22,
no. 12, pp. 2288 2292.
Likewise were obtained the other oxiranes V, VI,
VIII whose constants are given in Table 1.
5. Allakhverdiev, M.A., Khalilova, A.Z., Farzali-
ev, V.M., and Sultanov, Yu.M., Khim. Geterotsikl.
Soed. 1988, no. 5, pp. 598 602.
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1,2-Epithio-4-phenylbutane (XI). Into a three-
neck flask was charged 76 g (1 mol) of thiourea and
30 ml of sulfuric acid solution containing 1 g-equiv of
the acid and 350 ml of water. At vigorous stirring the
reaction mixture was cooled to 5 10 C and maintain-
ing this temperature 148 g (1 mol) of 1,2-epoxy-4-
phenylbutane was added dropwise within 2 h. After
completion of oxirane addition the reaction mixture
was stirred for 1 h at room temperature and then
hydrolyzed with a solution of 106 g (1 mol) of
sodium carbonate in 450 ml of water. The organic
layer was separated, the water layer was twice
extracted with ether. The combined organic solutions
were dried with anhydrous sodium sulfate. After
removing ether the reaction product was subjected to
vacuum distillation to obtain 116 g (71%) of com-
pound XI, bp 129 C (2.5 mm Hg), n2D0 1.5625;
1H NMR spectrum (CCl4), , ppm: 1.85, 2.25 (2H,
CH2-thiirane), 2.85 m (1H, CH), 2.75 t (2H, CH2Ar),
6.85 s (5H, C6H5); 13C NMR spectrum (CDCl3), ,
ppm: 35.36 (CH), 25.94 (CH2-thiirane), 141.08 (Ci),
128.41, 128.36 (C°,m), 125.97 (Cp), 38.29 (CH2 Ph),
35.60 (CH2 CH). Found, %: C 73.31; H 7.12; S
19.16. C10H12S. Calculated, %: C 73.12; H 7.36;
S 19.52.
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