Regiochemistry of cleavage of monosubstituted oxiranes by phosphorochloridites. Enantiomeric composition of oxiranes by 31P NMR spectral data

Article abstract of DOI:10.1023/A:1020815410142

The regioisomeric composition of the adducts of unsymmetrical oxiranes with achiral and chiral phosphorochloridites was studied. Factors allowing enantiomeric assessment of chiral oxiranes with the aid of chiral derivatizing organophosphorus reagents were

Full text of DOI:10.1023/A:1020815410142

Russian Journal of General Chemistry, Vol. 72, No. 8, 2002, pp. 1207 1214. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 8, 2002,
pp. 1288 1295.
Original Russian Text Copyright
2002 by Bredikhina, Novikova, Azancheev, Bredikhin.
Regiochemistry of Cleavage of Monosubstituted Oxiranes
by Phosphorochloridites. Enantiomeric Composition
31
of Oxiranes by P NMR Spectral Data
Z. A. Bredikhina, V. G. Novikova, N. M. Azancheev, and A. A. Bredikhin
Arbuzov Institute of Organic Chemistry, Kazan Research Center,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
Received October 27, 2000
Abstract The regioisomeric composition of the adducts of unsymmetrical oxiranes with achiral and chiral
phosphorochloridites was studied. Factors allowing enantiomeric assessment of chiral oxiranes with the aid of
chiral derivatizing organophosphorus reagents were revealed.
One of the most promising applications of organo-
phosphorus compounds is their use as reagents for
enantiomeric assessment of chiral organic compounds
[1]. Chiral phosphorus(III) chlorides have most fre-
quently been employed as such reagents, and active
compounds with an X H function (X = O, N, S), as
substrates. Along with reactions with alcohols, amines,
and thiols, PIII chlorides characteristically enter reac-
tions with oxiranes [2 4], leading to -chloroalkyl
phosphites. It can be assumed that were the phos-
phorus component chiral, the resulting diastereomeric
phosphites would have different 31P NMR spectra, and
these differences could be used for enantiomeric
assessment of chiral epoxides. In the present work we
examined this possibility. As chiral substrates we took
monosubstituted oxiranes.
their studies on reactions of polychlorides (PCl3,
PhPCl2, Et2NPCl2, etc.) with propylene oxide. Ho-
wever, they, too, did not directly analyze reaction
mixtures. Assuming complex reaction patterns of
polychlorides with oxiranes, we restricted ourselves to
phosphorous ester monochlorides.
First we reacted racemic oxiranes Ia Ie with
achiral phosphorochloridites IIa IIc.
Additions of PIII monochloro derivatives can give
two regioisomers. Certain aspects of the regioche-
mistry of such reactions have first been discussed in
[5 8] as far back as 1960s. We considered it necessary
to touch upon this problem.
Addition of PIII chlorides to monosubstituted
oxiranes most frequently [3] involves epoxide ring
cleavage by the C O bond at a primary carbon atom.
However, Pudovik and Faizullin [6] reported the
additions of ethyl phosphorochloridite to styrene and
divinyl oxides, occurring in preference to cleavage of
the C O bond at a secondary carbon atom.
The weakness of preceding works concerned with
the regiochemistry of oxirane ring cleavage is that
they all contain no quantitative data on the isomeric
composition of the resulting products and no direct
evidence for the structure of the isomers. Obereigner
et al. [9, 10] performed quantitative GLC analysis in
The reactions were performed in methylene chlo-
ride with cooling. Immediately after reaction comple-
tion, the reaction mixtures were analyzed by 31P NMR
1070-3632/02/7208-1207$27.00 2002 MAIK Nauka/Interperiodica

1208
BREDIKHINA et al.
Table 1. Chemical shifts in the 31P NMR spectra and relative contents [ P, ppm (%)] of regioisomeric phosphites III and
IV, obtained by reaction of oxiranes Ia Ie with achiral phosphorochloridites IIa IIc
IIa
IIb
IIc
Oxirane
III
IV
III
IV
III
IV
Ia
Ib
Ic
Id
Ie
138.55 (87)
137.91 (7)
139.29 ( 100)
138.51 (82)
139.11 (77)
138.28 (13)
138.01 (93)
129.18 (86)
127.14 (5)
126.65 (76)
129.33 (75)
129.02 (70)
127.16 (14)
127.27 (95)
128.34 (24)
126.64 (25)
126.85 (30)
130.06 (81)
121.25 ( 0)
131.17 (97)
131.47 (92)
128.69 (76)
127.31 (19)
127.45 ( 100)
128.67 (3)
127.09 (8)
132.08 (24)
139.29 (18)
138.44 (23)
Table 2. Chemical shifts in the 31P NMR spectra, diastereomeric dispersions of chemical shifts, and relative contents of
regioisomeric phosphites [ P, ppm,
P, ppm (%)] obtained by reaction of chiral phosphorochloridites IId IIf and
oxiranes Ia Ie
IId
IIe
IIf
Oxirane
III
IV
III
IV
III
IV
Ia
Ib
143.32, 143.43, 142.50, 142.64, 137.66, 138.35, 136.88, 0 (11) 141.24, 142.58, 137.17, 137.28,
0.11 (73) 0.14 (27) 0.69 (89) 1.34 (80) 0.11 (20)
142.18, 142.52, 141.99, 142.34, 131.26, 138.00, 136.22, 136.43, 140.49, 147.08, 137.36, 138.38,
0.34 (3)
0.35 (97)
6.74 (3)
0.21 (97)
6.59 ( 0)
1.02 ( 100)
Ic
142.70 (94)
142.51, 0.00 (6) 138.39 ( 100)
141.31 ( 100)
Id
142.99, 143.10, 142.29, 142.40, 139.17, 139.69, 141.17,
0.11 (93) 0.11 (7) 0.52 (78) 0.00 (22)
143.01, 143.30, 142.89, 143.25, 138.39, 138.99, 135.44, 135.52, 144.25, 144.90, 135.17, 0.00 (7)
0.29 (74) 0.44 (26) 0.60 (97) 0.08 (3) 0.65 (93)
144.36, 146.27, 137.75,
1.91 (87) 0.00 (13)
Ie
spectroscopy. Except for the 31P NMR spectra of the
reaction mixtures of oxide Ic with phosphorochlori-
dite IIa and of oxide Ib with phosphorochloridite IIc,
which contain a single phosphite signal (Table 1), the
other spectra contain two signals whose integral in-
tensity ratio was used for isomeric assessment of the
reaction products.
benzo-1,3,2-dioxaphospholane (IIc), we observed in
the spectrum a new signal at 121.25 ppm, along
P
with the signal at
127.45 ppm. To obtain con-
clusive evidence for tPhe structure of the major isomer
resulting from reactions of phosphorochloridites with
oxide Ib, the latter was reacted with phosphorochlo-
ridite IIc on a preparative scale to isolate an indivi-
dual reaction product. Simultaneously, from 2-chloro-
ethanol and the same phosphorochloridite IIc we
prepared isomer III. The aliphatic fragment of isomer
Assignment of signals to one or another regio-
isomer is difficult without additional evidence, since
even within one series the signals of the major and
minor components can trade places. The regioisomers
were identified by the following procedure.
III gives a triplet at
48.4 (CH2Cl) and a doublet at
C
61.9 ppm (OCH) in the 13C NMR spectrum. The
C
same fragment of the styrene oxide adduct gives a
doublet at C 60.8 (CHCl) and a triplet at C 67.8 ppm
(OCH2). These spectral data provide unambiguous
evidence showing that the latter reaction product has
structure IV.
In separate experiments we reacted phosphoro-
chloridites IIa IIc with alcohols RCH(OH)CH2Cl
(R = Me, Ph, ClCH2). Thus obtained solution of
phosphites III was added to a corresponding reaction
mixture, and its 31P NMR spectrum was measured
again. The signal whose intensity had increased was
assigned to isomer III. Upon addition of phosphite III
to the reaction mixture of oxide Ib with 2-chloro-4,5-
Regioisomeric assessment of the phosphites ob-
tained from epoxides Id and Ie was perfomed, first,
by analogy with other reaction products and, second,
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REGIOCHEMISTRY OF CLEAVAGE OF MONOSUBSTITUTED OXIRANES
1209
relying on the results of their reactions with chiral
phosphorochloridites (see below).
additional problems associated with configurational
changes in the course of reaction. Earlier we brought
in reactions with achiral alcohols cyclic phosphoro-
chloridites IId IIf obtained from L-tartaric acid [12]
and (R)-2,2 -dihydroxy-1,1 -binaphthyl [13]. Reagent
IId was first proposed in [14].
As seen from Table 1, reactions of unsymmetrical
epoxides with phosphorous ester monochlorides yield
a mixture of two regioisomers. One of the isomers is
always preferred, but its structure and relative content
are strongly dependent on the nature of the reagents.
Irrespective of the mechanism of addition of phos-
phorus chlorides to epoxides, cleavage of the C O
bond with a terminal (primary) carbon atoms remains
the initial conformation of the carbon chiral center
intact, while the resulting phosphite III proves to be
homochiral to the parent epoxide and preserves its
enantiomeric composition. By contrast, the absolute
configuration amd enantiomeric purity of regioiso-
meric phosphites IV depend on the mechanism of
C O bond cleavage with a central (secondary) carbon
atom. Therefore, the enantiomeric composition of the
alcohol fragment in phosphites IV is unsuitable for
enantiomeric assessment of the parent epoxide. As
noted above, regioisomeric phosphites III and IV are
impossible to identify by their 31P NMR chemical
shifts. Other spectral methods, too, are hardly suitable
for this purpose, because the resulting spectra are
quite complex; in any case, invoking other techniques
is time-consuming. Note that the adducts of phos-
phorochloridites with epoxides are not too stable and
undergo rearrangements with time [5 8]. Staying in
the framework of 31P NMR, one can try to make use
of chiral characteristic of regioisomers for their
identification.
As primary alcohols V we used (S)-( )-2-methyl-1-
butanol (Va), rac-4-hydroxymethyl-2,2-dimehyl-1,3-
dioxalane (Vb), and rac-2,3-epoxy-1-propanol (Vc)
and as secondary alcohols, rac-2-butanol (Vd), rac-1-
phenylethanol (Ve), l-menthol (Vf), and d-borneol
(Vg). Unfortunately, with enantiomerically pure phos-
phorochloridites IId IIf we failed to determine
P
for enantiomerically pure Va, Vf, and Vg in the cited
works, which makes the selection even poorer. There-
fore, here we additionally synthesized racemic phos-
phorochloridites from racemic tartaric acid and (R)-
2,2 -dihydroxy-1,1 -binaphthyl. Table 3 lists the result-
Regioisomers III and IV formed by reactions of
chiral racemic epoxides I with chiral phosphorochlori-
dites with a single chirality element (or with a group
of chirality elements related by axial symmetry) each
should be a mixture of diastereomers, and, therefore,
the 31P NMR spectrum should contain up to four
signals. The difference in the chemical shifts of dia-
stereomers ( P) is called diastereomeric dispersion
of chemical shift [1, 11]. The value of P depends on
the distance between chiral fragments and an indicator
atom (here 31P nucleus). In regioisomers III, the
indicator atom is separated from the chirality center
by two bonds, and in regioisomers IV, by three.
ing
values, as well as the mean
values for
P
P
primary and secondary alcohols reacted with each
chiral phoshorus reagent.
It should be noted that
depends on many fac-
of
tors, including solvent. AccorPding to [15], the
P
the adduct of methylene phosphorochloridite and rac-
2,2 -dihydroxy-1,1 -binaphthyl in THF is 14.03 ppm.
The adduct obtained in [15] is fully identical to adduct
VI of phoshorochloridite rac-IIf and menthol Ve,
whose
in toluene is 5.54 ppm. Such a radical dif-
P
Expected
mated by comparing the
values for these two cases can be esti-
P
ference prompted us to repeat the experiment in THF.
The chemical shifts of diastereomeric phosphites VI
values of phosphites ob-
P
tained from chiral phosphorus and alcohol com-
ponents.
proved to be 149.74 and 155.22 ppm (
5.48 ppm).
P
The respective values for the adduct of phosphite IIf
with glycidol Vc in THF were found to be 136.71 and
Chirality analysis by means of organophosphorus
compounds is most conveniently performed with
cyclic molecules whose chiral organic fragment
possesses axial symmetry, since here the indicator
phosphorus atom remains achiral and creates no
138.59 ppm (
tained in THF are close to those in toluene (Table 3).
Thus, the values of 14.03 ppm is obviously
errorneus. As Pa rule, solvent much less affects
1.88 ppm). Both
values we ob-
P
P
P
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BREDIKHINA et al.
Table 3. Diiastereomeric dispersions of chemical shift
P, ppm) in the 31P NMR spectra of diastereomeric
and give a single, nonsplit signal in the 31P NMR
spectrum.
(
phosphites obtained by reactions of primary (Va Vc) and
secondary (Vd Vg) alcohols with chiral phosphorochlori-
dites IId IIfa
As follows from Table 2, the
values for the
diastereomeric pairs of isomers III Pand IV of the
adducts of oxiranes Ia Ic with phosphorochloridites
(Table 2) are either comparable for both regioisomers
or, as would be expected, those for regioisomer III are
much higher. Therefore, we can assign with assurance
Alcohol
IId
IIe
IIf
Va
Vb
Vc
0.02
0.42
1.16
0.53
0.25
1.05
0.08
1.09
0.62
0.00
0.00
0.20
0.07
0.81
7.84
2.60
3.32
3.64
0.08
0.88
2.04
1.00
0.06
7.07
5.54
3.02
3.92
the signals at
1.91 ppm) and the signals at
144.90 ppm (
adducts of IIf with oxiranes Id and Ie to regioisomers
III. The signals of regioisomers IV at 137.75 (
144.36 and 146.27 ppm (
P
P
144.25 and
0.65 ppm) in the Pspectra of the
P
mean
Vd
Ve
Vf
Vg
P
P
0) and 135.17 ppm (
0) are almost nonsplit. In
value
both cases, isomer III P with a largest
P
prevails. The same is true of the adducts of oxirane Id
and phosphorochloridite IIe and of oxirane Ie and
phosphorochloridite IIe. We suppose these fundings
give sufficient grounds to state that all reactions of
glycidyl ethers and esters with phosphorochloridites
occur in preference to cleavage of the C O bond with
a terminal (primary) carbon atom.
mean
a
For reagents IId and IIe in THF and for reagent IIf in toluene.
that the character of chiral environment of the indi-
cator atom.
As seen from Table 3, the mean P value for each
reagent IId IIf in the group of primary alcohols is
lower than in the group of secondary alcohols. Con-
sequently, the distance of the chiral center from the
indicator atom is a factor useful for regioisomeric
assessment of -chloroalkyl phosphites III and IV.
However, one should exercise caution in each case
and take account of dissymmetry features of substrates.
Whereas the dissymmetry degree is difficult to estimate
quantitatively, it is intuitively obvious that the more
similar the chemical environments of the chiral
centers, the closer the quantitative manifestations of
Together data in Tables 1 and 2 enable us to
answer most questions as to the possibility and re-
liability of enantiomeric assessment of chiral epoxides
by means of 31P NMR spectroscopy with use of chiral
derivatizing organophosphorus reagents like IId IIf.
As seen from these data, the regiochemistry of phos-
phorochloridite addition to monosubstituted oxiranes
generally follows common regularities of electrophilic
additions (if, at least formally, one considers the
phosphorus atom as electrophile). The overall reliabi-
lity of the analysis is increased with increasing in-
tensity of signals to be analyzed. In view of the above
statement that one should take account of the charac-
teristics of regioisomers III only, we are skeptical in
advance of the attempts to analyze oxiranes with
substituents efficiently stabilizing a neighboring
cation (like Ph, CH2=CH, etc.), since here the fraction
of the required regioisomer is too small. On the
contrary, strong - and/or -acceptor substituents
ensure preferential formation of the required regio-
isomer, thus giving stronger grounds for achieving
success.
the chirality phenomenon. The
estimated using data in Table 3.
values can be
P
Table 2 lists the 31P NMR data for the reaction
mixtures of racemic oxiranes Ia Ie with chiral cyclic
phosphorochloridites IId IIf. The reactions with
compounds IId and IIe were performed in THF, and
the reactions with compound IIf, in toluene. The pairs
of signals of diastereomers of each regioisomer are
readily identified by their close intensities. In Table 2,
the regioselectivities of the reactions (percentages of
isomers III and IV) are characterized by the integrated
intensities of signals of both diastereomers. The regio-
isomeric adducts of phosphorochloridites IId IIf with
oxiranes Ia Ic were identified in the same way as
with dialkyl phosphorochloridites IIa IIc, i.e. by
As seen from Table 2, the
values sometimes
P
vary in parallel with the difference in the chemical
shifts of regioisomeric phosphites III and IV, which
may result in overlap of signals, as, for instance, in
addition to the mixtures of a known isomer. Identifica- Fig. 1a. The signals of racemic oxirans (and/or
tion of the adducts of epichlorohydrin (Ic) with chiral
phosphorochloridites is facilitated by the fact that the
central atom in isomers III loses chirality. As a result,
their isomers are no longer subject to diastereomerism
racemic phosphorochloridites) are easier to identify
relying on the close intensities of signals in either
diastereomeric pair. Thus, as seen from Fig. 1a, the
pair of lower intensity signals with a larger P relates
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REGIOCHEMISTRY OF CLEAVAGE OF MONOSUBSTITUTED OXIRANES
1211
III
143.01
143.30
139.69
III
139.17
IV
IV
IV
142.89
143.25
141.17
(a)
(b)
143.5 143.0 142.5 142.0 141.5 141.0 140.5 140.0 139.5 139.0 P, ppm
31
Fig. 1. P NMR spectra of the reaction mixtures of (a) glycidyl acetate (Ie) and 2-chloro-(4R, 5R)-diethoxycarbonyl-1,3,2-
dioxaphospholane (IId) and (b) glycidyl 1-naphthyl ether (Ie) and 2-chloro-(4R, 5R)-bis(N,N-dimethylaminocarbonyl)-1,3,2-
dioxaphospholane (IIe).
to isomer IV, while the pair of strong signals relates
to the major isomer III. When both components,
oxirane and phosphorochloridite, are scalemic (i.e.
enriched with one of the enantiomers or enantio-
merically pure), the theoretically possible four signals
will have different intensities, thus complicating
interpretation. Therefore, even if the signals of regio-
isomers do not overlap (Fig. 1b), preliminary analysis
of racemic samples makes sence, facilitating inter-
pretation of the spectra of scalemic adducts.
Note that the difference in the values of the
regioisomers of the cyclic phosphorochloridite ob-
tained from diol IIf is larger than P. The case in
point is that this value is larger in absolute value
than all respective values for reagents derived from
The synthesis remains the chiral center intact, and,
therefore, oxirane R-If should preserve the enantio-
meric composition of the parent alcohol. From a
racemic starting material, a racemic glycidyl phos-
phite was obtained.
P
P
The spectrum of the reaction mixture of rac-If and
tartaric acid. Earlier [13] we revealed a pronounced (4R,5R)-IId is given in Fig. 2a. The diastereomers of
diastereoselectivity of reaction of diol IIf with chiral
alcohols. The adverse effect of the latter factor is
readily bypassed by using excess phosphorochloridite,
which ensures complete reaction of the substrate.
the major regioisomer give signals at
142.61 ( 0.42 ppm, phosphorus atom in a chiral
heterocycle) and 127.56, 127.46 ppm (
phosphorus atom in the pyrocatechol fragment). The
respective signals of the minor ( 12%) regioisomer
143.03,
P
P
0.10 ppm,
P
The procedure of enantiomeric assessment can be
exemplified by a scalemic oxirane o-phenylene
glycidyl phosphite (If). This oxirane was prepared
from (S)-glycidol (ee 90.0%) and o-phenylene
phosphorochloridite.
are at
130.64 ppm (
142.03, 141.83 (
0.20 ppm) and 130.77,
P
P
0.13 ppm).
P
We showed above that glycidol ethers take up
phosphorochloridites to give regioisomers III as
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BREDIKHINA et al.
S-III
III
142.61
III
III
143.04
143.03
127.60
127.56
127.46
IV
IV
130.77
(a)
130.64
142.03
141.83
IV
R-III
142.63
144
141.89
142
130
128
(b)
IV
130.50
144
142
140
132
130
128
P, ppm
31
Fig. 2. P NMR spectra of the adducts of (a) 2-chloro-(4R,5R)-diethoxycarbonyl-1,3,2-dioxaphospholane (IId) with rac-2-
(2,3-epoxypropoxy)-4,5-benzo-1,2,3-dioxaphospholane (rac-If) and (b) of chlorophosholane IId and epoxyphospholane R-If.
major products; therefore, the stronger signals we rules of electrophilic addition. In the case of chiral
assigned to these isomers. Further evidence for such
assignment comes from the fact that the major isomer
phosphorochloridites, the 31P NMR signals of the
regioisomeric phosphites resulting from these reac-
tions can be differentiated by the regioisomeric dis-
persion of chemical shifts, which most frequently is
larger for the isomers formed by C O bond clevage
at a primary carbon atom in the parent oxirane. The
preferential formation of such regioisomers from
monosubstituted epoxides makes favorable prerequisi-
tes for enantiomeric assessment of the latter by means
of 31P NMR spectroscopy with use of chiral derivatiz-
ing organophosphorus reagents.
has a larger
cycle.
of the phosphorus atom in the chiral
P
The spectrum of the scalemic sample (Fig. 2b)
contains only five defined peaks, since the signals of
the minor diastereomers of the minor regioisomer IV
are on the background level, while the signal of the
minor diastereomer at
127.6 ppm overlaps with
P
the signal of the major isomer because of the small
value. At the same time, the pair of downfield
sigPnals assignable to the phosphorus atom in a chiral
heterocycle of diastereomeric phosphites III can
be integrated. The relative integral intensities of these
pair of signals are I1 18.02 and I2 1.00. From here, the
enantiomeric purity of the oxirane in question can be
EXPERIMENTAL
The NMR spectra were measured on Varian T-60
(1H, 60 MHz) and Bruker MSL-400 (13C, 100.6 MHz;
31P, 161.92 MHz) spectrometers against internal TMS
(1H, 13C) and external H3PO4 (31P) in CDCl3 (1H, 13C),
CH2Cl2, THF, or toluene (31P).
estimated at 89.5% [ee = (I1
I2)/(I1 + I2)].
Thus, the regiochemistry of addition of phosphoro-
chloridites to unsymmetrical oxiranes follows general
The optical rotation was measured on a Polamat A
polarimeter.
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REGIOCHEMISTRY OF CLEAVAGE OF MONOSUBSTITUTED OXIRANES
1213
Commercial chemical grade propylene oxide (Ia)
and epichlorohydrin (Ic) were distilled before use.
1 h. The precipitate of triethylamine hydrochloride
was filtered off, the solvent was removed, and the
residue was fractionated in a vacuum to isolate 0.72 g
(64%) of 2-(2-chloro-1-phenylethoxy)-4,5-benzo-1,3,2-
dioxaphospholane, bp 170 171 C (0.2 mm), nD20
1.5770. 1H NMR spectrum, , ppm: 3.92 d (1H,
Styrene oxide (Ib) was obtained from styrene ac-
cording to [16], 1-naphthyl glycidyl ether (Id), from
epichlorohydrin according to [17], and glycidyl
acetate (Ie), from glycidyl mesylate according to [18].
2-(2,3-Epoxypropoxy)-4,5-benzo-1,3,2-dioxaphos-
pholane (If) were obtained according to [19]; com-
pound (R)-Ie, bp 85 90 C (0.07 mm), n2D0 1.5405, d420
1.3022, [ ]2D0 2.47 (without solvent), was obtained
in a similar way from (S)-glycidol (ee 90.0 %) which
we obtained earlier [20].
3
3
CH2Cl, JHH 6.0 Hz), 3.95 d (1H, CH2Cl, JHH
3
3
7.4 Hz), 5.00 d.d (1H, OCH, JHH 6.0, JHH 7.4 Hz),
7.00 7.20 m (4H, C6H4), 7.36 br.s (5H, Ph). 13C
NMR spectrum, C, ppm: 48.42 (CH2Cl), 61.87
(OCH); 113.22 (o-CH), 123.50 (p-CH), 144.21 (Cipso
)
(C6H4), 127.43 (o-CH), 128.81 (m-CH), 129.14
(p-CH), 138.17 (Cipso, Ph).
1-Chloro-2-propanol was prepared from allyl chlo-
ride [21]. 2-Chloro-1-phenylethanol was prepared
from styrene [22] and contained up to 10% of 2-
chloro-2-phenylethanol. 1,3-Dichloro-2-propanol was
prepared according to [23].
REFERENCES
1. Hulst, R., Kellogg, R.M., and Feringa, B.L., Recl.
Trav. Chim. Pays-Bas, 1995, vol. 114, no. 4/5,
pp. 115 138.
Reaction of oxiranes Ia If with phosphorochlo-
ridites IIa IIf. Oxirane Ia If, 2 mmol, was added with
shaking under dry argon at 5 10 C to a solution of
2.2 mmol of freshly distilled phosphorochloridite
Ia Ic in 2 ml of CH2Cl2 or to a solution of phosphoro-
chloridite Id, If (prepared by the procedure in [12])
in 5 ml of THF, or to a solution of 2.2 mmol of
phosphorochloridite If (prepared by the procedure in
[13]) in 6 ml of toluene. The reaction mixture was left
to stand for 30 min at room temperature and placed
into an ampule for measuring its 31P NMR spectrum.
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Reaction of 2-chloro-4,5-benzo-1,3,2-dioxaphos-
pholane (IIc) with styrene oxide (Ib). A solution of
1.11 g of oxide Ib in 4 ml of CH2Cl2 was added
dropwise under dry argon with stirring (5 C) to a
solution of 1.62 g of acid chloride IIc in 8 ml of
CH2Cl2. The mixture was left to stand at room tem-
perature for 1 h, the solvent was removed, and the
residue was fractionated in a vacuum to isolate 1.7 g
(62%) of 2-(2-chloro-2-phenylethoxy)-4,5-benzo-
1,3,2-dioxaphospholane, bp 141 145 C (0.01 mm),
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no. 10, pp. 2225 2230.
n2D0 1.5810. H NMR spectrum, , ppm: 3.87 p. t (2H,
1
3
3
POCH2, JPH 7.0, JHH 7.0 Hz), 4.82 t (1H, CHCl,
3JHH 7.0 Hz), 6.83 7.08 m (4H, C6H4), 7.31 br.s (5H,
C6H5). 13C NMR spectrum, C, ppm: 60.85 (CHCl),
67.76 (OCH2), 112.14 (o-CH), 122.95 (p-CH), 145.48
(Cipso), (C6H4), 127.45 (o-CH), 128.68 (m-CH),
128.86 (p-CH), 137.44 (Cipso, Ph).
11. Bredikhin, A.A., Bredikhina, Z.A., Gaisina, L.M.,
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Reaction of 2-chloro-4,5-benzo-1,3,2-dioxaphos-
pholane (IIc) with 2-chloro-1-phenylethanol. A solu-
tion of 0.67 g of acid chloride IIc in 2 ml of diethyl
ether was slowly added under dry argon at 5 C to a
mixture of 0.46 g of 2-chloro-1-phenylethanol and
0.39 g of triethylamine in 8 ml of diethyl ether. The
mixture was left to stand at room temperature for
13. Bredikhin, A.A., Bredikhina, Z.A., and Nigmatzya-
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otravlyayushchikh veshchestv (Synthesis of Poisons),
Moscow: Oborongiz, 1939, p. 44.
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 8 2002