Reaction of 4-(N,N-Dimethylaminophenyl)magnesium Bromide with Palladium Tetrakis(triphenylphosphine)

Article abstract of DOI:10.1023/A:1025592320130

(α-Chloroalkyl)thiiranes react with sodium phenolates at heating in water-alcohol mixtures furnishing phenoxymethylthiiranes, 3-phenoxythietanes (resulting from thiirane-thietane rearrangement), or their mixture. The increased polarity of solvent favors t

Full text of DOI:10.1023/A:1025592320130

Russian Journal of Organic Chemistry, Vol. 39, No. 2, 2003, pp. 226
2003, pp. 249 257.
Original Russian Text Copyright © 2003 by Tomashevskii, Sokolov, Potekhin.
-234. Translated from Zhurnal Organicheskoi Khimii, Vol. 39, No. 2,
-
To the memory of A.A.Petrov
Reaction of 4-(N,N-Dimethylaminophenyl)magnesium Bromide
with Palladium Tetrakis(triphenylphosphine)*
A. A. Tomashevskii, V. V. Sokolov, and A. A. Potekhin
St. Petersburg State University, St. Petersburg, 198504 Russia
Received October 15, 2002
Abstract¾ -(a -Chloroalkyl)thiiranes react with sodium phenolates at heating in water-alcohol mixtures furnis hing
phenoxymethylthiiranes, 3-phenoxythietanes (resulting from thiirane-thietane rearrangement), or their mixture. The
increas ed polarity of solvent favors the thiirane-thietane rearrangement. 2,2-Dimethyl-3-(chloromethyl)thiirane forms
an exclusion for it does not afford (phenoxymethyl)thiirane even in anhydrous ethanol. Diastereomeric erythro- and
threo-(1-chloroethyl)thiiranes react stereospecifically giving 2-methyl-3-phenoxymethylthiiranes or 2-methyl-3-
phenoxythietanes of trans- and cis -configuration respectively. Specific features of these reactions are discussed from
the viewpoint of solvent polarity effect on the competition between formal chlorine substitution along “recyclization”
mechanism or through thiirane-thietane rearrangement.
We established previously that epithiohalohydrins
and their simplest homologs reacted with morpholine
through a mechanism of cycle opening cycle closure
(«recyclization») of the thiirane ring affording at equi-
molar amount of reagents rearranged (morpholi-
nomethyl)thiiranes similar to behavior of epihalo-
hydrins [2].
are formed in reactions of thiolates [4- 9], secondary
amines [9, 10], N,N-dialkyldithiocarbamates [11], and
alcoholates [12, 13]. Thietanes formation was first re-
vealed in reactions with alkali [14] and salts of carbox-
ylic acids [15]. Further studies showed that with such
nucleophiles as phenolates [3], N,N-dialkyldithio-
phosphates [16- 18], and thioacetates [15] arose both
thiiranes and thietanes depending on the conditions. It
was presumed that the structure of the product origi-
nated from different directions of thiirane ring opening
in different media: in water at the secondary, and in
aprotic solvents at the primary carbon atom, and this
behavior was ascribed to dissimilar character of
thiirane (I) solvation. However this assumption on the
different places of ring opening of the thiirane ring was
disproved, for the later data [2, 19] indicated that the
ring opened at the primary carbon atom. Detailed ki-
netic study of (chloromethyl)thiirane solvolysis in
aqueous dioxane demonstrated that the reaction corre-
sponded to SN1 mechanism [8].
At the same time (chloromethyl)thiirane (I) is
known to react fairly unusual with harder nucleophiles
of phenol type providing either arylthioglycidyl ethers
(II), or 3-phenoxythietanes (III), or mixtures thereof
depending on the reaction conditions [3].
The latter direction, the so-called thiirane-thietane
rearrangement, is quite unexpected in the epihalo-
hydrin series. In the general case the course of the
process is governed both by the character of nucleo-
phile, polarity of solvent, and the nature of the leaving
group.
In this connection the target of this study is acquisi-
tion of new data on reaction mechanism of (a -
chloroalkyl)thiiranes and phenolate anions and inves-
tigation of new synthetic opportunities of the thiirane-
thietane rearrangement. One problem concerns the elu-
cidation whether exists a possibility of (phenoxy-
methyl)thiiranes formation by an attack of the phe-
nolate anion on the atom 2 of the intermediately arising
The reaction may occur either giving rise to
thiiranes, or to thietanes, or to their mixture. Thiiranes
____________
*
For communication II see [1].
1070-4280/00/3902-0226$25.00 Ó 2003 MAIK [ Nauka/Interperiodica ]

227
REACTIONS OF (a -HALOALKYL)THIIRANES WITH NUCLEOPHILIC REAGENTS: III.
1-thioniabicyclobutane (path b), or its opening always
occurs at the central C- S bond (path a) giving rise to
both thiirane and thietane formed simultaneously. Here
the distribution of the label in the (phenoxy-
methyl)thiirane would suggest whether the thiirane
formation be an independent process [in case of label
transition to the exocyclic carbon atom of the
(phenoxymethyl)thiirane, (path c)], or occurs a concur-
rent opening of thioniabicyclobutane in both directions
(paths a and b).
The thiirane/thietane ratio we planned to measure
by GLC. Therefore we synthesized individual unla-
beled (phenoxymethyl)thiirane (II) and 3-phenoxythie-
tane (III). Thiirane II was obtained from glycidyl
phenyl ether (V) via isothiuronium salt (s). 3-Phen-
oxythietane (III) was obtained by treating thiirane I
with aqueous sodium phenolate [3]. The ratio of these
products strongly depeds on the solvent, and the mix-
ture thiirane/thietane of desired ratio according to [3]
3-phenoxythietanes, and (phenoxymethyl)tiiranes are
generated independently.
As the easiest way to clear this problem we re-
garded a reaction of 2-(chloromethyl)thiirane-3,3-d2
(Ia) [2] with sodium phenolate under conditions where
________________________________
Table 1. 1H NMR spectra of solutions of 3-phenoxythietanes III, X, XII, XVIa, b in CDCl3, d, ppm, J, Hz
Compd.
R1
R2
R3
R4
R5
H arom
2J12
3J13
3J23
3J34
3J35
2J45
4J
no.
IIIa
X
XII
3.56
3.09
1.45
4.23
4.11
1.53
3.36
3.90
1.61
1.63
1.34
3.87
5.28
1.73
4.91
4.98
4.68
5.32
3.36
3.09
3.56
3.90
7.1–7.7
7.1–7.7
7.1–7.7
7.1–7.7
7.1–7.7
7.1–7.7
9.8
9.7
–
7.9
–
7.6
–
7.6
–
7.9
–
9.8
9.7
–
1.7
–
–
–
–
8.0
8.0
3.25
b
b
b
b
b
XVIa
XVIac
XVIb
6.0
6.5
6.9
–
–
–
–
–
–
–
1.7
3.49
3.04
3.34
3.53
3.22
3.65
7.2
–
–
7.8
8.1
7.8
8.4
7.8
8.3
9.5
a
b
c
The spectrum was recorded at operating frequency 100 MHz.
Coupling constants not determined.
The spectrum was recorded in C6D6 solution.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 2 2002

TOMASHEVSKII et al.
Table 2. 13C NMR spectra of 3-phenoxythietanes III, X, XII, XVIa, b, d, ppm, J, Hz
228
Compd. no.
III
R1
R2
R3
C2
C3
C4
C arom
–
–
–
35.7
40.0
56.3
47.2
45.6
74.1
80.3
78.3
78.4
71.6
35.7
40.0
31.1
32.5
33.0
115.2, 121.6, 129.7, 156.5
118.5, 121.7, 129.2, 154.5
115.3, 121.3, 129.4, 156.9
115.3, 121.4, 129.5, 156.6
114.7, 121.2, 129.5, 156.6
X
XII
XVIa
XVIb
–
30.5
–
–
23.3
–
–
24.3
21.4
–
16.8
–
should form in acetonitrile. However under these con-
ditions we obtained and identified by GLC as the only
product thiirane II. The reaction carried out in anhy-
drous ethanol also furnished only thiirane II although
in [3] was indicated that here thietane III should be the
prevailing product. In this situation we were obliged to
chose the proper solvent by ourselves; it turned out to
be 85% aqueous ethanol. The ratio of compounds
II/III in the product was according to GLC 5 : 2, con-
venient for the analysis of the spectra. In this connec-
tion we are obliged to mention that the analytical pro-
cedure used in [3] to determine the composition of re-
action mixture obviously gave incorrect results (it was
based on «selective» iodometric titration of thiiranes
[3]). Actually 3-aryloxythietanes form only in the pres-
ence of water; in all anhydrous solvents, even in alco-
hols, arise only thiiranes and products of their further
transformations. This is due apparently to stringent re-
quirements of 1-thioniabicyclobutane toward solvation.
13C NMR spectrum of the obtained mixture of products
IIa, and IIIa unambiguously showed that the label
was transmitted into the a -position with respect to the
thiirane ring, thus evidencing insignificant role of
path b.
(chloromethyl)thiirane
(VI),
2,2-dimethyl-3-
(chloromethyl)thiirane (VII), and diastereomeric
erythro- and threo-(a -chloroethyl)-thiiranes (VIII) and
(IX) with phenolate anion in water-alcohol mixtures of
various compositions.
Reaction of thiirane VI with sodium phenolate
even in anhydrous ethanol gave rise only to 3-methyl-
3-phenoxythietane (X) which structure nambiguous-
ly follows from its 1H and 13C NMR spectra
(Tables 1, 2).
1
In the H NMR spectrum of thietane X appears a
singlet from three protons of a methyl group (d 1.73
3
ppm) and AÂ system with JHH 9.7 Hz from nonequiva-
lent protons at C2 and C4 (Ha' and Hå') belonging to
thietane ring (d 3.09–3.90 ì.ä.). In the upfield region
of the 13C NMR spectrum are present only three signals
of carbon atoms. The mass spectrum is also consistent
with the structure of 3-methyl-3-phenoxythietane (X):
the lack of a peak with m/z [M- 33] is unusual for
thiiranes but common for thietanes[20].
+
Thus (phenoxymethyl)thiiranes form independent of
3-phenoxythietanes, and as in the case of N-nucleo-
philes the reaction proceeds through «recyclization»
mechanism.
Thiirane VII in reaction with sodium phenolate in
water-alcohol mixtures of various compositions
(50- 100% of ethanol) furnished a mixture of two com-
pounds in 1: 1 ratio, insensitive to the ethanol-water
ratio. It was first assumed that the products mixture
It was reasonable to assume that introduction of ad-
ditional substituents (in the simplest case methyl
groups) both into the thiiraane ring proper and into
a -position to it would affect both the selectivity and
rate of reactions between (a -haloalkyl)thiiranes and
nucleophiles. However we could not predict the extent
of such influence: the homologs of (chloro-
methyl)thiirane we were the first to synthesize, and
comparison with oxygen-containing analogs not al-
ways suggested correct prediction of behavior of sulfur
analogs. In order to elucidate the character of this in-
fluence we studied the reaction of the simplest ho-
mologs of (chloromethyl)thiirane (I): 2-methyl-2-
contained
2,2-dimethyl-3-(phenoxymethyl)thiirane
(XI) and thietane (XII).
However it seemed dubious because of nearly com-
plete insensitivity of the products ratio to the solvent
composition: with (chloromethyl)thiirane (I) in its re-
action with phenolate the influence of the medium
character on the ratio of products is very pronounced.
Besides thiirane XI might arise here only from direct
replacement of chlorine because the «recyclization»
mechanism for 2,2-dimethyl-3-(chloromethyl)thiirane
(VII) is inconsistent with Krasusky rule. The products
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 2 2002

229
REACTIONS OF (a -HALOALKYL)THIIRANES WITH NUCLEOPHILIC REAGENTS: III.
mixture was separated by means of preparative TLC on
The 13C and 1H NMR spectra of the second product
lack carbon and proton signals belonging to the
1
silica gel. Analysis of H and 13C NMR spectra of the
1
products revealed that one of them actually was 2,2-di-
methyl-3-phenoxythietane (XII). Its 1H NMR spectrum
contains a system AX2, where a signal of d 4.91 ppm
phenoxy group. The H NMR spectrum is consistent
with a structure containing a 3-methyl-2-butenyl frag-
ment where the signal of a single olefin proton is split
with an extremely characteristic remote coupling con-
3
(1H, JHH 8 Hz) obviously corresponds to the proton
attached to C3 of the thietane ring, but not to methylene
protons of the phenoxymethylene group (their reso-
nances are located in the region 3.5-4.5 ppm). The
mass spectrum is consistent with structure XII for it
lacks a peak of m/z [M–33]+characteristic of thiirane
spectra.
stant JHH 1 Hz. In the 1 3C NMR spectrum appears
4
a set of five signals: two downfield and three
upfield. It may be stated basing on these data and also
on the mass spectrum of the compound (m/z 202,
[M]+· ) that it is bis(3-methyl-2-butenyl) disulfide
(XIII).
The way of its generation can be suggested only
tentatively. An example is known of dechlorination of
compound XIV at its treating with a base (apparently
as a result of a halophilic attack) [21].
Probably in our case occurs the following process.
According to data of [22] compound XV at room
temperature spontaneously rearranges into disulfide
XIII.
erythro-Diastereomer VIII in anhydrous ethanol fur-
nishes one product (see scheme).
It was identified as thietane (XVIa) proceeding
1
1
Very peculiar route takes reaction with sodium phe-
from the data of 13C and H NMR . Firstly, in the H
nolate of diastereomeric thiiranes VIII and IX.
NMR spectrum appears a signal at d 4.98 ppm charac-
Scheme.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 2 2002

TOMASHEVSKII et al.
230
teristic of a proton attached to C3 atom of a 3-phenoxy-
substituted thietane, but not of methylene protons of
(phenoxymethyl)thiirane (d 3.4-4.5 ppm). This signal
looks like a «correct quartet»,3JHH 7.6 Hz in C6D6 ex-
cluding both structure XVIIIa where the most de-
shielded proton of the PhO-CH-Me moiety should ap-
pear as a signal of five lines, and structure XVIIa in
whose spectrum any of the methylene protons from the
phenoxymethyl group at thiirane ring should be split
either into a doublet of doublets or into a triplet. How-
ever sometimes a doublet of doublets looks like a quar-
tet. Then we would be obliged to decide that the sec-
ond proton of the methylene group has a signal at d
3.04 or 3.22 ppm that is quite unreasonable for a
phenoxymethyl group. The 13C NMR spectrum also
testifies to thietane structure XVIa. In a 2,3-di-
substituted thiirane XVIIa the chemical shifts of the
carbon atoms in the ring according to our data should
fall into the range 35-40 ppm and have very close val-
ues. Unlike that in thietane XVIa the difference be-
tween the chemical shifts of carbons C2 and C4 should
be significantly greater, as it is actually observed (d
32.5 and 47.2 ppm respectively). Mass spectrum of the
compound is in agreement with the structure of
thietane XVIa. It does not contain a peak of m/z [M–
33]+ that is unusual for thiiranes, and the fragmentation
of its molecular ion has the pattern that we already
have observed for thietanes X and XII (see
EXPERIMENTAL). The trans-configuration of the
thietane XVIa obtained we may now only suggest pro-
ceeding from the known stereochemistry of oxirane-
oxetane rearrangement observed on erythro-a -
methylglycidyl 2,4-dinitrobenzoate [23]. Constant of
the coupling between protons attached to C2 and C3 of
the thietane ring (3JHH 7.2 Hz, C6D6) in this case does
not permit determination of compound XVIa configu-
ration with the use of the known Karplus expression.
The application of Overhauser effect also did not pro-
vide unambiguous result due to the spatially close posi-
tion of all the protons in the ring.
pholine [2] we can state that the obtained 2-methyl-
3(phenoxymethyl)thiirane (XVIIb) has cis-
configuration. There are no reasons why the stereo-
chemistry of “recyclization” mechanism should change
to the opposite in going from amine to phenolate anion.
It is confirmed by coupling constant of the protons at-
tached to C2 and C3 of the thiirane ring having the
value of 6.6 Hz in CDCl3 and 6.8 Hz in C6D6.
It should be noted that for compounds IX and X in
strongly polar proton solvents sharply grows the prob-
ability of direct chlorine replacement as compared to
the «recyclization» mechanism due to more efficient
solvation of the charged intermediate state.
Thiirane IX afforded thietane XVIb (with 10% im-
purity of thiirane XVIIb) only in 50% aqueous metha-
nol. The 13C NMR spectrum of the minor component
completely coincided with thaat of thiirane XVIIb. The
XVIIIb structure should be rejected because the signal
of the methine proton of the phenoxyethyl group would
be a multiplet of no less than five lines. Taking into
account the structure of the initial thiirane and the
mechanism of rearrangement [23] we assume for ob-
tained thietane XVIb the cis-configuration. Here like in
the case of thietane XVIa the coupling constant be-
tween the protons at C2 and C3 atoms permits no un-
ambiguous conclusion with respect to the configuration
of compound obtained. The use of Overhauser effect
also did not allow uniquely determined result.
However some reasons indicate the validity of the
assumptions on the configurations of the corresponding
thietanes. Firstly, it is the fact of formation of thiirane
XVIIb and not thietane XVIb from threo-thiirane IX
in the anhydrous ethanol medium. Let us consider the
intermediate of the thiirane-thietane rearrangement,
1-thioniabicyclobutane, for each instance.
Reaction of threo-diastereomer IX with sodium
phenolate in anhydrous ethanol also furnished a single
product. In the 13C NMR spectrum recorded in the
DEPT 135 mode in the upfield region appear in differ-
ent phases signals of d 15.7, 35.0 and 36.4 ppm on the
one sude and of d 67.9 on the other side. The latter sig-
nal can be definitely assigned only to the carbon atom
of the methylene group of the phenoxymethylene
fragment in XVIIb structure.Taking into account the
mechanism of reaction between thiirane IX and mor-
It is seen that in the case of threo-diastereome IX in
the intermediate IXa exists a destabilizing repulsion
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 2 2002

231
REACTIONS OF (a -HALOALKYL)THIIRANES WITH NUCLEOPHILIC REAGENTS: III.
between the pseudoaxial proton at C4 and pseudoaxial
methyl group attached to C. This interaction should
aldehydes (XIX), (XX), and also 4-(thietan-3-yloxy)-
benzoic acid (XXI) and its methyl ester XXII.
2
increase the energy of intermediate IXa as compared to
that of diastereomeric intermediate VIIIa arising from
erythro-diastereomer VIII. Since the initial thiranes
VIII and IX are approximately equal in energy the dif-
ference in the energy of the intermediates should affect
¹
the value DDG in keeping with Hammond postulate.
The solvation in anhydrous ethanol is insufficiently
efficient for the rearrangement to occur in the case of
thiirane IX, but is amply enough for rearrangement in
the reaction of erythro-diastereomer VIII. In a water-
methanol solution the solvation is more strong , and
thiirane-thietane rearrangement occurs also with threo-
thiirane IX.
X = 3-CHO (XIX), 4-CHO (XX), 4-CO2H (XXI), 4-CO2Me
(XXII).
EXPERIMENTAL
1H and 13C NMR spectra were registered on spec-
trometer Bruker AC 200 at operating frequencies 200
and 59.28 MHz respectively from solutions in CDCl3
with HMDS as internal reference (if not indicated oth-
erwise). In description of DEPT 135 spectra «+» means
positive phase (methyl or methine carbon atom), “- ”
means negative phase (methylene carbon atom), ”q”
means a lack of DEPT signal (quaternary carbon
atom). Mass spectra were measured on GC-MS instru-
ment LKB 2091S, ionizing electrons energy 70eV,
ionization current 25mA, accelerating voltage 35 kV,
separator temperature 150°C, temperature of ion source
150°C. Glass column 1800 ´ 2 mm, stationary phase
2% SE-30 on Chromosorb W (80-100 mesh). Oven
temperature 50- 150°C, vaporizer temperature 200°C.
Carrier gas helium, flow rate 30 ml/min. Elemental
analyses were carried out on C,H,N-analyzer Hewlett-
Packard HP-185B. Reaction progress was monitored
and the purity of substances was checked by GLC on
chromatograph LKhM-80 equipped with glass columns
2000´ 3 mm, stationary phase 5% SE-30 on Chroma-
trone Super 0.125- 0.160 mm and 5% XE-60 on Chro-
matrone N-AW 0.16-0.20 mm; carrier gas helium, flow
rate 39 ml/min, detector katharometer. The identifica-
tion of compounds was performed on two columns.
Preparative thin-layer chromatography (PTLC) was
carried out on silica gel 40- 160 mesh.
Secondly, the remote coupling constant observed in
1
the H NMR spectrum of 2-methyl-3-phenoxythietane
(XVIb) obtained from threo-thiirane IX may originate
from spin-spin coupling of the W-type in the envelope
4
conformation, i.e. we are dealing with J2e',4e'. This is
possible if exist conformations A and B in thietanes
XVIa and XVIb respectively.
However the B conformation of trans-isomer XVIa
is a lot less favorable than the A conformation of cis-
isomer XVIb due to pseudoaxial location of the
phenoxy and methyl groups. In the cis-isomer the cor-
responding A conformation is more feasible because
the phenoxy group takes the pseudoequatorial position,
and occurrence of configuration with W-type coupling
between the protons at C2 and C4 seems more probable.
To show the practical application of this rear-
rangement to organic synthesis we prepared sev-
eral 3-(aryloxy)thietanes. It should be noted that a
series of similar compounds was synthesized be-
fore [3], but there were used the simplest phenoles
(mono- and polyhalo-substituted, cresols, and
methoxyphenols). Besides no information was
published on the yields and constants of the com-
pounds obtained (save the data on 3-phen-
oxythietane), and identification of the substances
was performed basing on the elemental analyses
for the products of their oxidation, sulfones. In this
study we prepared 3 and 4-(thietan-3-yloxy)benz-
(Chloromethyl)thiirane
(I),
2-(chloromethyl)-
thiirane-3,3-d2 (Ia), 2-methyl-2-(chloromethyl)thiirane
(VI), 2,2-dimethyl-3-(chloromethylthiirane (VII), and
diastereomeric racemic erythro- and threo-1-
(chloroethyl)thiiranes (VIII) and (IX) were prepared
along published procedures [2].
S-(2-hydroxy-3-phenyloxypropyl)isothiuronium
sulfate (IV). In a mixture of 3 ml (0.06 mol) of concn.
H2SO4 and 40 ml of water was dissolved at heating
8.4 g (0.11 mol) of thiourea, the mixture was cooled to
10°C, and to the dispersion obtained was added drop-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 2 2002

TOMASHEVSKII et al.
232
13C NMR spectrum (25.142 MHz, CDCl3), d, ppm
of compound IIa: 23.8, 31.3, 71.9 ê (J 24 Hz), 114.8,
121.3, 129.4, 158.6.
wise 15 g (0.1 mol) of phenyl glycidyl ether (V). The
mixture was then stirred at cooling with ice water for
20 min. The precipitate was filtered off and washed on
the filter first with ice water and then with cold ace-
tone. Yield 26 g (98%). T. decomp. > 300°C.
3-Methyl-3-phenoxythietane (X). To a solution of
1.15 g (9 mmol) of thiirane II in 5 ml of 96% ethanol
was added a solution of sodium phenolate [0.95 g (10
mmol)] of phenol and 0.22 g (9.5 mmol) of sodium] in
20 ml of 95% ethanol. The mixture was heated at re-
flux to complete disappearance of the original thiirane
(GLC monitoring, about 40 min). Ethanol was evapo-
rated, the reaction product was extracted into ether, the
combined extract were washed with 5% solution of
KOH, with saturated solution of NaCl, and dried with
sodium sulfate. Ether was evaporated, the residue was
distilled. Yield 1.0 g (61%), bp 95–100°C (1.5 mmHg.),
nD20 1.5666. Mass spectrum, m/z (Irel, %): 180 [M]+· (3),
94 (28), 87 (100), 65 (9), 59 (10), 53 (13), 47 (9), 45
(25), 41 (13), 39 (24). Found, %: C 56.68; H 9.63.
C10H12OS. Calculated, %: C 56.78; H 9.53.
(Phenoxymethyl)thiirane (II). To a suspension of
26 g (0.1 mol) of salt IV in 110 ml of water was added
dropwise at stirring a solution of 11 g (0.08 mol) of
K2CO3 in 50 ml of water within 10 min. Then the mix-
ture was stirred for 10 min at 50°C, 50 ml of benzene-
pentane mixture, 1:1, was added, and the stirring was
continued for 40 min. The organic phase was sepa-
rated, the water phase was extracted with benzene. The
combined organic solutions were dried by sodium sul-
fate. The solvents were distilled off, the residue was
distilled . Yield 11.5 g (70%), bp 100–101°C (2 mm
Hg), nD201.5778. Published data [24]: bp 106°C (1 mm
Hg), nD20 1.5735. H NMR spectrum (100 MHz, CCl ),
1
4
d, ppm: 2.12 d.d (1H, J 1.0, J 4.5 Hz), 2.40 d.d (1H, J
1.0, J 6.1 Hz), 2.83 m (1H), 3.66 d.d (1H, J 7.0, J 10.0
Reaction of thiirane (VII) with sodium phe-
nolate. To a solution of sodium phenolate [0.35 g (15
mmol) of sodium and 1.6 g (17 mmol) of phenol] in 30
ml of 96% ethanol at 60°C was added dropwise within
30 min a solution of 20 g (15 mmol) of thiirane VII in
5 ml of 96% ethanol. The mixture was heated at reflux
on a water bath for 2 h. The ethanol was distilled off in
a vacuum, and the residue was diluted with 5 ml of wa-
ter. The reaction product was extracted into ether, the
extract was washed with 5% water solution of KOH
and dried with sodium sulfate. On evaporation of ether
1.2 g was obtained of a mixture containing 2,2-
dimethyl-3-phenoxythietane (XII) and bis(3-methyl-2-
butenyl) disulfide (XIII) at molar ratio 1 : 1 (GLC).
The mixture was separated by PTLC method (eluent
Hz), 4.06 d.d (1H, J 5.4, J 10.0 Hz), 7.1–7.7 m (5H).
13C NMR spectrum (25.142 MHz, CDCl3), d, ppm3.8,
31.4, 72.6, 114.8, 121.3, 129.6, 158.5.
3-Phenoxtthietane (III). To a solution of 14.1 g
(0.15 mol) of phenol and 6.0 g (0.15 mol) of NaOH in
20 ml of H2O at stirring within 30 min was added 16.3
g (0.15 mol) of thiirane I. The mixture was stirred for 2
h at 70°C, cooled, extracted with ether, the extracte
was washed with 5% water solution of NaOH, with
water, and dried with Na2SO4. The ether was distilled
off, the residue was subjected to distillation. Yeidl 6 g
(24%), bp100–101°C (2 mm Hg), mp 39–40°C. Pub-
lished data [3]: bp 130–140°C (12 mm Hg), mp 39°C.
Reaction of 2-(chloromethyl)thiirane-3,3-d2 (Ia)
with sodium phenolate. To emulsion of 4,8 g (44
mmol) of thiirane Ia in 30 ml of 85% (by volume)
aqueous ethanol was added dropwise while stirring at
44-45°C within 1 h a solution of 44 mmol of sodium
phenolate [1.05 g (44 mmol) of sodium and 4.18 g
(44 mmol) of phenol] in 30 ml of 85% ethanol. Ethanol
was distilled off at reduced pressure, to the residue was
added 20 ml of water, the mixture was extracted with
ether, the extract was washed with 50 ml of 5% cold
solution of KOH, with saturated solution of Na2SO4
till neutral washings, and dried with Na2SO4. The ether
was removed, the residue was distilled. Yield 2.3 g
(30%), bp 100–105°C (2 mmHg). We obtained a
mixture of 2-(phenoxymethyl)thirane-d2 (IIa) and
3-phenoxythietane-d2 (IIIa) in molar ratio 5 : 2 (GLC).
ether-pentane, 1 : 3). Mass spectrum of compound XII,
m/z (Irel., %): 194 [M] (3), 101 (100), 94 (57), 85
(13), 67 (33), 65 (13), 59 (44), 55 (14), 45 (13), 41
+·
(26), 39 (24); m* 34.5, 44.6. (XIII). Mass spectrum of
+·
compound XIII, m/z (Irel., %): 202 [M] (3), 101 (20),
94 (14), 69 (100), 68 (24), 67 (35), 53 (27), 43 (12), 41
(87), 40 (14), 39 (33).
trans-2-Methyl-3-phenoxythietane (XVIa). To a so-
lution of sodium phenolate [0..5 g (22 mmol) of sodium
and 2.35 g (25 mmol) of phenol] in 50 ml of anhydrous
ethanol while boiling at reflux was added within 5 min
dropwise a solution of 2.45 g (20 mmol) of thiirane VIII
in 10 ml of anhydrous ethanol. The boiling of the mixture
was continued for 2 h more, ethanol was distilled off, and
the residue was diluted with 10 ml of water and extracted
with ether. The extracts were combined, washed with
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 2 2002

233
REACTIONS OF (a -HALOALKYL)THIIRANES WITH NUCLEOPHILIC REAGENTS: III.
5% solution of KOH, and dried with sodium sulfate.
The ether was distilled off, and the residue was sub-
90% (by volume) aqueous methanol was added drop-
wise while stirring at 45- 55°C within 1.5 h a (chloro-
methyl)thiirane (0.09 mol). After the end of addition the
stirring of the heterogeneous mixture was continued for
2 h at the same temperature. Then the reaction mixture
slowly cooled, and therewith the reaction product pre-
cipitated as crystals. It was filtered off, washed on the
filter with water till neutral washings, and recrystallized
from an appropriate solvent.
jected to distillation. Yield 1.0 g (28%), bp 98- 105°C
+·
(1.5 mm Hg). Mass spectrum, m/z (Irel., %): 180 [M]
(20), 94 (21), 88 (9), 87 (100), 77 (9), 59 (12), 53 (13),
47 (9), 45 (37), 39 (13). Found, %: C 59.00; H 10.00.
C11H14OS. Calculated, %: C 58.76; H 9.86.
cis-2-Methyl-3-phenoxythietane (XVIb). To a so-
lution of sodium phenolate [0..4 g (10 mmol) of NaOH
and 1.0 g (11 mmol) of phenol] in 50% aqueous
methanol heated at reflux was added within 5 min
dropwise a solution of 0.3 g (2..5 mmol) of thiirane IX
in 5 ml of 50% aqueous methanol. The mixture was
refluxed for another 1 h, the methanol was distilled off,
the reaction product was extracted into ether, the ex-
tract was washed with 15% solution of NaOH, the
ether was evaporated, and water was distilled off with
benzene (20 ml). The residue was distilled. Yield 0.2 g
(44%), bp 73- 75°C (1.5 mm Hg). A mixture of com-
3-(Thietan-3-yloxy)benzaldehyde (XIX). Yield
61%, mp 41–43°C (from aqueous EtOH), bp 141–
143°C (1.5 mm Hg). 1H NMR spectrum, d, ppm: 3.41–
3.46 m (2H), 3.56–3.62 m (2H), 5.37 quintet (1H, J 7.3
Hz), 6.92 d (2H, J 8.8 Hz), 7.84 m (1H, J 9.8 Hz), 9.89
s (1H). 13C NMR spectrum, d, ppm: 35.8 (–), 72.0 (+),
113.8 (+), 122.6 (+), 124.7 (+), 130.8 (+), 138.3 (q),
157.3 (q), 192.2 (+). Found, %: C 62.06; H 5.16.
C10H10O2S. Calculated, %: C 61.83; H 5.19.
4-(Thietan-3-yloxy)benzaldehyde (XX). Yield
69%, mp 54–56°C (from aqueous EtOH), bp 145–
147°C (1.5 mm Hg). 1H NMR spectrum, d, ppm: 3.40–
3.47 m (2H), 3.57–3.65 m (2H), 5.40 quintet (1H, J
10.9 Hz), 7.12 d.t (1H, J 2.0, J 7.3 Hz), 7.29 m (1H),
7.38–7.52 m (2H), 9.97 s (1H).13C NMR spectrum, d,
ppm: 35.6 (–), 71.9 (+), 115.6 (+), 130.9 (q), 132.5 (+),
161.6 (q), 191.0 (+). Found, %: C 62.00; H 5.10.
C10H10O2S. Calculated, %: C 61.83; H 5.19.
pounds XVIb and XVIIb was obtained at molar ratio
+·
9:1 (1H NMR). Mass spectrum, m/z (Irel., %): 180 [M]
(8), 134 (3), 120 (5), 94 (15), 87 (100), 77 (2), 59 (3), 53
(11), 47 (2), 45 (28), 41 (2), 39 (11). Found, %: C 58.06;
H 9.66. C10H12OS. Calculated, %: C 58.76; H 9.86.
cis-2-Methyl-3-(phenoxymethyl)thiirane (XVIIb).
To a solution of 1.2 g (10 mmol) of thiirane IX in 5 ml
of anhydrous ethanol at reflux was added dropwise
within 15 mim a solution of sodium phenolate [0.15 g
(11 mmol) of sodium and 1.2 g (13 mmol) of phenol]
in 7 ml of anhydrous ethanol. The boiling mixture was
refluxed for 30 min more, ethanol was evaporated, the
residue was diluted with 10 ml of 10% water solution
of NaOH and extracted with ether. The combined ex-
tracts were washed with 10% water solution of NaOH
and dried with CaCl2. The ether was distilled off, and
the residue was subjected to distillation. Yield 0.75 g
Methyl 4-(thietane -3-yloxy)benzoate (XXI). Yield
1
68%, mp 66–68°C (from aqueous EtOH). H NMR
spectrum, d, ppm: 3.39–3.47 m (2H), 3.57–3.64 m
(2H), 3.90 s (1H), 5.38 quintet (1H, J 7.6 Hz), 6,84 d (2H,
13
J 7.6 Hz), 8.00 d (2H, J 8.6 Hz). C NMR spectrum, d,
ppm: 35.7 (–), 52.3 (+), 71.8 (+), 114.9 (+), 123.8 (q),
132.2 (+), 160.4 (q), 167.1 (q). Found, %: C 59.09; H
5.55. C11H12O3S. Calculated, %: C 58.91; H 5.39.
4-(Thietane -3-yloxy)benzoic acid (XXII) was ob-
tained by alkaline hydrolysis of ester XXI followed by
treating the reaction mixture with hydrochloric acid.
Yield 93%, mp 211-213°C (from BuOH). 1H NMR
spectrum, d, ppm: 3.40–3.55 m (4H), 5.41 quintet (1H,
J 7.3 Hz), 6.87 d (2H, J 8.9 Hz), 7.86 d (2H, J 8.9 Hz),
11.7–12.8 br.s (1H, COOH).13C NMR spectrum, d,
ppm: 35.6 (–), 71.7 (+), 115.1 (+), 124.8 (q), 132.2 (+),
160.0 (q), 167.5 (q). Found, %: C 57.09; H 4.65.
C10H10O3S. Calculated, %: C 57.13; H 4.79.
(42%), bp 95–97°C (2 mm Hg), nD20 1.5630. H NMR
1
spectrum, d, ppm: 1.54 d (3H, J 6.2 Hz), 3.13 quintet
(1H, J 6.3 Hz), 3.30 d.d.d (1H, J 5.2, J 6.6, J 8.5 Hz),
3.93 d.d (1H, J 8.5, J 10.4 Hz), 4.38 d.d (1H, J 5.2, J
13
10.1 Hz), 7.1–7.7 m (5H). C NMR spectrum, d, ppm:
15.7 (+), 35.0 (–), 36.4 (+), 67.9 (–), 114.6 (+), 121.1
(+), 129.4 (+), 158.4 (q). Mass spectrum, m/z (Irel, %):
180 [M]+· (5), 149 (16), 94 (100), 87 (97), 77 (14), 71
(5), 69 (4), 55 (37), 51 (11), 45 (37). Found, %: C 59.05;
H 9.99. C10H12OS. Calculated, %: C 58.76; H 9.86.
REFERENCES
3-(Aryloxy)thietanes. General procedure. To a so-
lution of an appropriate sodium phenolate (0.11 mol of
substituted phenol and 0.1 mol of NaOH) in 100 ml of
1. Tomashevskii, A.A., Sokolov, V.V. and Pote-
khin, A.A., Zh. Org. Khim., 1998, vol. 34, p. 618.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 2 2002

TOMASHEVSKII et al.
234
2. Tomashevskii, A.A., Sokolov, V.V. and Pote-
khin, A.A., Zh. Org. Khim., 1994, vol. 30, p. 1528.
3. Sander, M., Monatsch. Chem., 1965, vol. 96, p. 896.
M.A., Uch. zapiski Azerb. Inst. Nefti i Khimii, Ser.
Khim., 1978, p. 46.
14. Adams, E.P, J.Am.Chem.Soc., 1960, vol. 82, p. 2665.
4. Kuliev, A.M. and Guseinov K.Z., Prisadki k sma- 15. Ohta, H. and Ohta, M., Nippon Kagaku Zasshi, 1956,
zochnym maslam (Additeves to Lubrication Oils ),
Baku, 1967, p. 44.
5. Kuliev, A.M., Byashimov K., and Guseinov K.Z., Zh.
Org. Khim., 1972, vol. 8, 2256.
vol. 77, p. 198; Chem. Abstr . 1958, vol. 52, 253f.
16. German Patent 1186712, 1961; Ref. Zh. Khim., 1962,
19L 292.
17. Nuretdinova, O.N. and Arbuzov, B.A., Izv. Akad.
Nauk SSSR, Ser. Khim. 1968, p. 2318.
18. Nuretdinova, O.N., Arbuzov B.A., and Guseva F.F.
Izv. Akad. Nauk SSSR, Ser. Khim., 1976, p. 662.
19. Fokin, A.V. and Kolomiets, A.F., Khimiya tiiranov
(Thiiranes Chemistry ), Moscow: Nauka, 1978, p. 198.
20. Sarkisov, Yu.S., Zenkevich, Yu.G., Rodin, A.A.,
V'yunov, K.A., and Bakhmedov, V.B., Khim. Get-
erotsikl. Soed., 1988, p. 739.
6. Nuretdinova, O.N. and Arbuzov B.A., Izv. Akad.
Nauk SSSR. Ser. Khim., 1972, p. 550.
7. US Patent 3728371, 1973; Chem. Abstr ., 1973, vol.
79, p. 5246a.
8. Morita, H. and Oae, S., Heterocycles, 1977, vol. 6,
p. 1593.
9. Stewart, J.M ., J. Org. Chem., 1964, vol. 29, p. 1655.
10. Garamanov, A.M., Bairamov G.K., Sultanov R.A.,
Monomery i polimery (Monopmers and Polymers), 21. Lautenschlaeger, F., J. Org. Chem., 1969, vol. 34,
Baku. 1983, p. 77. p. 3998.
11. Culvenor, C.C., Davies W., Pausacker K.H. J. Chem. 22. Hofle, G. and Baldwin, J.E., J. Am. Chem. Soc., 1971,
Soc., 1946, p. 1150. vol. 93, p. 6307.
12. Sadykh-Zade, S.I., Dzhafarov, K.A., and Kyazimov, 23. Francl, M.M., Hansell, G., Patel, B.P., and Swin-
Sh.K., Uch. Zapiski Azerb. Univ., Ser. Khim., 1971,
p. 42.
dell, C.S., J. Am. Chem. Soc., 1990, vol. 112, p. 3535.
24. Schuetz, R.D. and Jacobs, R.L., J. Org. Chem., 1961,
vol. 26, p. 3467.
13. Shakhmaliev, A.M., Dzhafarov K.A., Agashkova
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 2 2002