New synthetic route and characterisation of phosphorus and arsenic heterocyclic compounds

Article abstract of DOI:10.1080/10426500214881

Herein we report synthetic routes for the preparation of 2-chloro-1,3,2-dioxarsenane 1, O,O′-bis(5,5-dimethyl-1,3,2-dioxarsenane)-2,2-dimethyl-1,3-propanediol 3, 2-chloro-1,3,2-dioxaphosphorinane 4, and 2-fluoro-1,3,2-dioxaphosphorinane 5. The new synthetic routes described here have the advantage to be simple, very clean and to lead to the desired compounds in very good yields. Compound 2-fluoro-1,3,2-dioxarsenane 2 also was prepared in good yield and is described here for the first time. Compounds 1-5 were fully characterized on the basis of NMR spectroscopic studies. Semi-empirical structural studies have been carried out and the results show that 1 and 2 exist as a mixture of two conformers, whereas only one conformer for 4 and 5 have been found. Variable temperature ¹H NMR studies reveal a fluxional behaviour for 1 and a mechanism for the inter-conversion between its two conformers is proposed.

Full text of DOI:10.1080/10426500214881

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New Synthetic Route and Characterisation of
Phosphorus and Arsenic Heterocyclic Compounds
Robson M. Matos a , Luiz Carlos Gomes de Lima a , Edward de Souza a , Ana Lúcia Americano
Barcelos de Souza a , Miriam Bernardes Gomes de Lima a & Délio Soares Raslan a
a Universidade Federal de Minas Gerais , Brazil
Published online: 27 Oct 2010.
To cite this article: Robson M. Matos , Luiz Carlos Gomes de Lima , Edward de Souza , Ana Lúcia Americano Barcelos
de Souza , Miriam Bernardes Gomes de Lima & Délio Soares Raslan (2002) New Synthetic Route and Characterisation
of Phosphorus and Arsenic Heterocyclic Compounds, Phosphorus, Sulfur, and Silicon and the Related Elements, 177:12,
2859-2870, DOI: 10.1080/10426500214881
To link to this article: http://dx.doi.org/10.1080/10426500214881
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Phosphorus, Sulfur and Silicon, 2002, Vol. 177:2859–2870
C
Copyright 2002 Taylor & Francis
1042-6507/02 $12.00 + .00
DOI: 10.1080/10426500290146901
NEW SYNTHETIC ROUTE AND CHARACTERISATION
OF PHOSPHORUS AND ARSENIC
HETEROCYCLIC COMPOUNDS
Robson M. Matos, Luiz Carlos Gomes de Lima,
Edward de Souza, Ana Lu´cia Americano Barcelos de Souza,
Miriam Bernardes Gomes de Lima, and De´lio Soares Raslan
Universidade Federal de Minas Gerais, Brazil
(Received 2 April 2002)
Herein we report synthetic routes for the preparation of 2-chloro-
1,3,2-dioxarsenane 1, O,O’-bis(5,5-dimethyl-1,3,2-dioxarsenane)-2,2-
dimethyl-1,3-propanediol 3, 2-chloro-1,3,2-dioxaphosphorinane 4, and
2-fluoro-1,3,2-dioxaphosphorinane 5. The new synthetic routes de-
scribed here have the advantage to be simple, very clean and to lead to
the desired compounds in very good yields. Compound 2-fluoro-1,3,2-
dioxarsenane 2 also was prepared in good yield and is described here
for the first time. Compounds 1–5 were fully characterized on the basis
of NMR spectroscopic studies. Semi-empirical structural studies have
been carried out and the results show that 1 and 2 exist as a mixture
of two conformers, whereas only one conformer for 4 and 5 have been
found. Variable temperature 1H NMR studies reveal a fluxional be-
haviour for 1 and a mechanism for the inter-conversion between its two
conformers is proposed.
Keywords: Arsenic; conformation; NMR studies; phosphorus; semi-
empirical calculations
INTRODUCTION
Heterocyclic compounds of the type shown in Scheme 1 are an important
class of compounds1 with wide application such as the development of
specific immunoassays for the detection of pesticides,2 polymerization
We thank FAPEMIG, FINEP, PRPq-UFMG, and CNPq-Brazil for the continuing sup-
port of this work. The authors thank Dr. Wagner Batista de Almeida for his kind permis-
sion to use the workstations and others computational facilities of the LQC-MM, UFMG.
Address correspondence to Robson M. Matos, Departamento de Qu´ımica, Instituto
de Cieˆncias Exatas, Universidade Federal de Minas Gerais, Av. Antoˆnio Carlos, 6627,
Pampulha, 31270-901, Belo Horizonte, MG, Brazil. E-mail: robson@dedalus.lcc.ufmg.br
2859

2860
R. M. Matos et al.
SCHEME 1
reactions,3,4 syntheses of naturally occurring lipids,5 and as a reagent
to analyse labile hydrogen functional groups on coal materials.6
Recently, we have shown that the chemistry of this kind of com-
pounds towards transition metal is very interesting, and much remains
to be investigated.7,8 However, it is necessary to develop new and sim-
ple synthetic routes that lead to this type of compounds in better yields.
We already have shown that 5-membered rings such as 2-chloro-1,3,2-
dioxaphospholane, 2-chloro-4,5-benzodioxaphospholane,9 and 2-chloro-
1,3,2-dithiaphospholane10 can be obtained in very good yields by treat-
ing the corresponding diol or dithiol with PCl3. More recently, we have
shown that 2-chloro-1,3,2-dithiastibolane can be formed via skeletal
substitution reaction.11 Now, we report new routes for the preparation
of 6-membered rings containing P and As and the preparation of the
novel 2-fluoro-5,5-dimethyl-1,3,2-dioxarsenane.
RESULTS AND DISCUSSION
SCHEME 2
a) 2-Chloro-5,5-dimethyl-1,3,2-dioxarsenane 1
Compound 1 has been prepared by treatment of AsCl3 with the diol
in the presence of triethylamine using ether as a solvent in 75%

Characterisation of Phosphorus and Arsenic Heterocyclic Compounds
2861
yield,12,13 and more recently Said et al.14 reported the preparation of
the same compound, in 95% yield, by treatment of the diol with AsCl3
in dichloromethane. Herein we report that addition of 2,2-dimethyl-
1,3-propanediol, as a solid, to neat AsCl3 affords 2-chloro-5,5-dimethyl-
1,3,2-dioxarsenane 1 as the only product, also in a very good yield (97%).
Compound 1 was formed as a mixture of two conformers, as evi-
1
denced by its 1H and 13C{ H} NMR studies. At room temperature, the
1H NMR spectrum of 1 shows one broad singlet at 3.87 corresponding
to methylene hydrogens and a singlet at 0.98 corresponding to the
methyl hydrogens. At 50 C the signal at 3.87 starts to split into two
doublets at 4.26 and 3.65, whereas the signal at 0.98 starts to split
into two singlets at 1.21 and 0.79 revealing a spectrum correspond-
ing to an [AA’BB’] spin system. Typically, hydrogens in axial positions
on cyclohexanes are more shielded than the equatorial hydrogens,15
however, studies on 1,3-dioxanes show the opposite result.16 This is be-
lieved to be caused by the interaction between the He and the p-orbital
of the oxygen atoms.17 A deshieldding of the axial hydrogens relative to
their equatorial counterparts also has been observed for six-membered
ring systems containing phosphorus18–20 and arsenic.21–23 In this case,
the effect might be caused by the presence of an axial halogen on phos-
phorus or arsenic. Based on this, the resonance signals at 0.79 and
1
3.65 on the H NMR spectrum of 1 are assigned to the equatorial
methyl group and equatorial hydrogens respectively.
1
The 13C{ H} NMR spectrum of 1 at room temperature also reveals
its fluxional behaviour since broad signals are observed. This spectrum
shows a singlet due to the CH3 groups at 21.70, and at 71.97 corre-
sponding to the CH2, and a rather broad singlet at 35.4 attributed to
the C(Me)2.
Aksnes and coworkers21–24 proposed that 1 could be present, in solu-
tion, as two different chair conformations, that is, the chlorine is on an
axial position in the more stable conformer and on an equatorial posi-
tion in the other conformer. Furthermore, they proposed an intermolec-
ular halogen exchange process to account for the fluxional behaviour
of 1, since it is a well known fact that the inversion energy barrier be-
tween the two conformers would be prohibitively high. On the other
hand, Arbuzov et al.25 showed that the similar 2-chloro-4-methyl-1,3,2-
dioxarsenane has a chair conformation with an axial chlorine and equa-
torial methyl, based on measurements of its dipole moments and Kerr
constants. All these hypotheses have been approached in this work, em-
ploying semi-empirical calculations, PM3, coordinate driving and con-
formational search resources. First of all, an intramolecular inversion
of 1 was simulated and, as expected, a very high inversion energy bar-
rier (110 kcal mol 1) was found. Attempt to simulate a reaction path

2862
R. M. Matos et al.
FIGURE 1 Lateral view of the chair (left) and the twisted-boat (right) con-
formers of 1.
involving an intermolecular chlorine exchange process leading to the
formation of an isomer with the chlorine on a equatorial position also
gives a high inversion energy barrier, up to 60 kcal mol 1. Due to these
results, a conformational search of 1 was carried out which pointed
to the existence of two conformers, that is, a chair and twisted-boat
(Figure 1). The energy for the process of conversion chair/twisted-boat
1
for 1 was found to be 7 kcal mol (Table I).
Further conformational searches employing ab initio quantum me-
chanical calculations, 3-21G* (Table II), gave the same results as the
semi-empirical approach, that is, the possible coexistence of the chair
and the twisted-boat conformers. However, attempts to unequivocally
characterize the transition state between them and to quantitate the
conformational energy barrier were not satisfactory with that basis
set.
b) 2-Fluoro-5,5-dimethyl-1,3,2-dioxarsenane 2
To the best of our knowledge this compound has not been reported before
and its synthesis is a modification of the procedure described by Verkade
et al.20 to prepare 2-fluoro-5,5-dimethyl-1,3,2-dioxaphophorinane 5. Ev-
idence that 2 exists as a mixture of two conformers in solution comes
1
from the H NMR spectrum at room temperature, which consists of
two subspectra corresponding to [AA’BB’] spin system. One of the sub
TABLE I Calculated PM3 Enthalpy of Formation
for the Conformers of 1
1
Conformer
Description
1H/(kcal mol
)
Maximum
Minimum
Transition state
Twisted-boat (bt)
Chair (ch)
50% bt-ch
120
124
117

Characterisation of Phosphorus and Arsenic Heterocyclic Compounds
2863
TABLE II Calculated ab initio Enthalpy of Formation for the Conformers
of 1
1
Conformer
Description
Energy/a.u.
1E/a.u.
1H/(kcal mol
)
Minimum
Maximum
Transition state
Chair (ch)
Twisted-boat (bt)
50% bt-ch
3024.11640
3024.10273
3024.09013
0
0
8.6
16.5
0.01367
0.026272
spectra shows two doublets at 4.33 and 3.63 attributed to Ha and
He respectively, and two singlets at 0.81 (equatorial CH3) and 1.25
(axial CH3). The other subspectrum shows two doublets at 4.30 and
3.51 (Ha and He) and two singlets at 0.78 (equatorial CH3) and 1.28
(axial CH3). Conformational studies for 2 employing semi-empirical
PM3 calculations have been carried out and the results were similar
to those found for 1, that is, a coexistence of a chair and a twisted-
boat conformers (Figure 2) with their conversion energy barrier around
1
12 kcal mol (Table III). Similarly to 1, conformation searches using
ab initio quantum mechanical calculations (3-21G*) presented the same
results as the semi-empirical approach (Table IV). Again, it was not pos-
sible, with that basis set, to unequivocally characterize the transition
state and to quantitate the conformational energy barrier between the
conformers.
Interestingly, no C–F coupling constants have been observed on the
1
13C{ H} NMR spectrum of 2, as observed for 5 (vide infra). This might
be due to the bigger size of the arsenic compared to the phospho-
rus atom. Likewise, the difference of size of oxygen and sulphur has
been used to account for the decrease of 2J(CP) found for 2-chloro-1,3,2-
dioxaphospholane (8.7 Hz)9 and for 2-chloro-1,3,2-dithiaphospholane
(2.2 Hz).10 The two singlets at
22.0 and
23.2 are attributed
FIGURE 2 Lateral view of the chair (left) and the twisted-boat (right) con-
formers of 2.

2864
R. M. Matos et al.
TABLE III Calculated PM3 Enthalpy of
Formation for the Conformers of 2
1
Conformer
Description
1H/(kcal mol
)
Maximum
Minimum
Transition state
Twisted-boat (bt)
Chair (ch)
50% bt-ch
157
163
152
respectively to the CH3 at the equatorial and axial positions. The
1
13C{ H} NMR spectrum of 2 also shows singlets at 33.6 (CMe2) and
72.8 (CH2).
c) O,O’-bis(5,5-dimethyl-1,3,2-dioxarsenane)-
2,2-dimethyl-1,3-propanediol 3
Said and coworkers14 recently have reported the preparation of 3 in a
low yield (40%) by treatment of 1 with sodium. The same group has also
reported that 3 was isolated along several impurities from the reaction
of 1 with cyclohexylamine.14 The synthetic method herein reported has
the advantage to be a very clean one and to give 3 in a very high yield
(96%). It consists of addition of neat AsCl3 to the solid 2,2-dimethyl-1,3-
1
propanediol. Compound 3 was characterized by 1H and 13C{ H} NMR
1
spectroscopy. The H NMR spectrum exhibits two doublets at 4.29
and 3.60 corresponding to the hydrogens from the OCH2 group on the
ring and a singlet at 3.91 due to the equivalent hydrogens from the
bridging OCH2 groups. The coupling constant between the axial and
equatorial hydrogens on the ring is 11.2 Hz. Three other singlets are
observed for 3 at 1.24, 0.77, and 0.99. The latter is attributed to
the equivalent CH3 groups in the bridge and the first two attributed
to the CH3 groups on the ring. The signals at 4.29 and 1.24 are
most likely to be due to the axial hydrogens from the OCH2 and from
1
the axial CH3 groups, respectively. The 13C{ H} NMR spectrum shows
signals at 72.3 and 72.2 corresponding to the CH2 on the ring
and in the bridge, respectively, according to the integration of these
peaks (4:2). The signals observed at 36.8 and 33.2 are attributed to
TABLE IV Calculated ab initio Enthalpy of Formation for the Conformers
of 2
1
Conformer
Description
Energy/a.u.
1E/a.u.
1H/(kcal mol
)
Minimum
Maximum
Transition state
Chair (ch)
Twisted-boat (tb)
50% bt-ch
2665.62450
2665.61822
2665.61058
0
0
3.9
8.7
0.00627
0.01392

Characterisation of Phosphorus and Arsenic Heterocyclic Compounds
2865
quaternary carbons and, by use of the integration of the peaks. The
first can be attributed to the bridging carbon, whereas the latter to the
carbons on the ring. Another way to undoubtedly attribute these two
signals would be by comparison with data found for 1. However, since 1
1
has a fluxional behavior and, unfortunately, a low temperature 13C{ H}
NMR spectrum has not been recorded, the attribution had to be made
based on the data found for its phosphorus analogue compounds 4 and
5 and for its closely related fluoro compound 2 (vide infra), which show
signals for the Me2C at 32.8, 32.4, and 33.6 respectively. Thus, one
would speculate that the signal at 33.2 corresponds to the quaternary
carbons on the ring whereas the signal at 36.8 is due to the quaternary
carbon on the bridge. From the integration of the peaks at 22.8, 21.8,
and 21.4 it can be said, undoubtedly, that the first two correspond to
the carbon of the methyl groups on the ring whereas the latter corre-
1
sponds to the one in the bridge. Unfortunately, our 13C{ H} NMR data,
with respect to the CH2 resonance signals, do not match those reported
by Said et. al14 ( 68.3 (bridge) and 71.2 (ring)). However, the authors
do not provide details such as the solvent used for the NMR spectrum.
d) 2-Chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane 4
Treatment of 2,2-dimethyl-1,3-propanediol with PCl3 affords the title
compound in 95% yield. Compound 4 has been prepared by treatment
of the diol with PCl3 in presence of pyridine and ether as a solvent,20
1
but the authors did not report the yield. The 31P{ H} NMR spectrum
of 4 shows a singlet at 145 and it is in accordance with data found
by others.20,25 Its 1H NMR spectrum corresponds to an [AA’BB’X] spin
1
system; the data are shown in Table V. The 13C{ H} NMR spectrum
of 4 shows two singlets at 22.4 and 22.3 corresponding to the CH3
groups, a doublet at 32.8 corresponding to the quaternary carbon and
another doublet at 70.8 due to the methylene carbon. The 2JCP (2.7 Hz)
and 3JCP (4.7 Hz) coupling constants are in the range expected for this
kind of compounds.
TABLE V 1H NMR Data for 4 and 5
4
5
0
=
=
4.30
3.56
9.46
0.90
0.10
3.11
1.62
4.10
3.43
9.12
0.85
0.35
2.85
2.52
H(a)
H(e)
H (a)
0
H (e)
0
0
JH(a)H(e) = JH (a)H (e)
0
JH(a)H (a)
0
JH(e)H (e)
0
JH(a)P = JH (a)P
0
JH(e)P = JH (e)P

2866
R. M. Matos et al.
FIGURE 3 Lateral view of 4.
Semi-empirical calculations, PM3, followed by conformational stud-
ies agreed with experimental data, leading to the conclusion that 4
resides only in a chair conformation at room temperature (1Hf = 169
1
˚
kcal mol ) with the chlorine in an axial position and 2.8 A from the
˚
axial hydrogens and 4.4 A from the hydrogens of the equatorial methyl
group (Figure 3). Both chair and twisted-boat conformations have been
reported for similar six-membered ring compounds, showing that the
their conformational properties will depend on heteroatoms and on the
group bonded through the phosphorus.26–28
e) 2-Fluoro-5,5-dimethyl-1,3,2-dioxaphosphorinane 5
Treatment of 4 with SbF3 affords 5 in 71% yield. The 31P{1H} NMR
spectrum of 5 consists of a doublet at 110 showing the expected P-F
coupling constant (1JPF = 1179.7 Hz). Its 1H NMR spectrum corre-
sponds to an [AA’BB’XY] spin system and data are shown in Table V.
FIGURE 4 Lateral view of 5.

Characterisation of Phosphorus and Arsenic Heterocyclic Compounds
2867
1
The 13C{ H} NMR spectrum of 5 shows two signals for the methyl
groups at 22.0 (singlet) and 22.4 (doublet). Since the signal at 22.4
corresponds to the axial CH3, it can be said that the coupling of this
signal is due to the phosphorus nucleus. The other signals observed at
1
the 13C{ H} NMR spectrum of 5 are as expected (vide infra).
Similar for compound 4, semi-empirical calculations, PM3, followed
by conformational studies agreed with experimental data, leading to
the conclusion that 5 would exist only in a its chair conformation at
room temperature, 1Hf = 220 kcal mol 1, with the fluorine in an ax-
˚
˚
ial position and 2.7 A from the axial hydrogens and 4.3 A from the
hydrogens of the equatorial methyl group (Figure 4).
CONCLUSIONS
We have shown that the synthetic routes developed for the preparation
of compounds 1–5 are simple, reliable, and lead to excellent yields of the
desired compound. Semi-empirical calculations show that the arsenic
compounds 1 and 2 exist as two conformers, in solution, whereas their
phosphorus analogues, 4 and 5, exist in only one conformation, consis-
tent with the NMR spectroscopic data. It is believed that the existence
of two conformers of 1 and 2 is due to the larger size of the arsenic atom
relative to phosphorus. We have shown that semi-empirical calculations
(PM3 method) can be used along with spectroscopic characterization
with success for this type of system.
EXPERIMENTAL
All reactions were carried out either under dry dinitrogen in Schlenk
tubes or by use of high-vacuum techniques. Glassware was flame-dried
in vacuum. 2,2-Dimethyl-1,3-propanediol, arsenic trichloride and phos-
phorus trichloride are commercially available from Aldrich, and only
the latter was purified prior to its use. (Caution: AsCl3 and the arsenic
compounds herein described must be manipulated in a well ventilated
hood, and one should avoid contact with the skin.) The NMR spec-
tra were recorded on a Varian VRX400 spectrometer at 400.13 MHz
1
for H, at 100.61 MHz for 13C and 376.5 MHz for 19F or on a Bruker
AC200 operating at 200.13 MHz for 1H and 81.02 MHz for 31P. A Bruker
BVT1000 variable temperature unit was used to control the tempera-
ture. All chemical shifts data are quoted in ppm with positive values
to high frequency of the indicated reference (external 85% H3PO4 for
31P; SiMe4 for 1H and 13C and CFCl3 for 19F) and corrected with respect
to the appropriate deuterium frequency. Coupling constants are quoted

2868
R. M. Matos et al.
in Hertz. The theoretical calculations were accomplished utilising the
SPARTANTM suite, V. 4.0, running on a IRIX 6.2 SILICON GRAPHICS
workstation.
Synthesis of 2-Chloro-5,5-dimethyl-1,3,2-dioxarsenane 1
To neat AsCl3(12.9 g, 71.2 mmol) was added, over a period of 5 min, 2,2-
dimethyl-1,3-propanediol (1.4 g, 13.5 mmol). The mixture was stirred
for 1 h and the excess of AsCl3 was distilled to afford pure 1 (2.8 g; 97%).
1
13C{ H} NMR data (100.61 MHz; CDCl3; 25 C): 21.7 (s; CH3); 35.4
(bs; C(CH3)2) 71.97 (s; CH2); 1H NMR data (400.13 MHz; CDCl3; 25 C):
0.98 (bs; CH3; 6H); 3.87 (bs; CH2; 4H); 1H NMR data (400.13 MHz;
CDCl3; 50 C): 0.79 (s; CH3(equatorial); 3H); 1.21 (s; CH3(axial) 3H);
3.65 (d; CH2(equatorial); 2H; 2JHH = 9.8 Hz); 4.26 (d; CH2(axial); 2H;
2JHH = 9.8 Hz).
Synthesis of 2-Fluoro-5,5-dimethyl-1,3,2-dioxarsenane 2
To a flask containing SbF3 (2.8 g, 15.5 mmol) 1 was added (3.3 g,
15.5 mmol) and the mixture stirred for 30 min. The product was dis-
1
tilled under reduced pressure to yield 2 (2.9 g, 75%). 13C{ H} NMR
data (100.61 MHz; CDCl3; 25 C):
CH3(equatorial)); 33.6 (s; C(CH3)2); 72.8 (s; CH2); H NMR data
(400.13 MHz; CDCl3; 25 C): 0.81 (s; CH3(equatorial); 3H); 1.25
22.0 (s; CH3(axial));
23.2 (s;
1
2
(s; CH3(axial); 3H); 3.63 (d; CH2(equatorial); 2H; JHH = 11.2 Hz);
4.33 (d; CH2(axial); 2H; 2JHH = 11.2 Hz); 19F{ H} NMR data (376.51
1
MHz ; CDCl3; 25 C): 44.5 (s).
Synthesis of O,O’-bis(5,5-dimethyl-1,3,2-dioxarsenane)-
2,2-dimethyl-1,3-propanediol 3
Neat AsCl3 (12.9 g, 71.6 mmol) was added to a flask containing 2,2-
dimethyl-1,3-propanediol (1.4 g, 13.5 mmol). The mixture was stirred
for 1 h, and the excess of AsCl3 was evaporated under reduced pres-
1
sure to yield a colorless oil (5.9 g, 96%). 13C{ H} NMR data (100.61
MHz; CDCl3; 25 C): 21.4 (s; CH3(bridge)); 21.8 (s; CH3(ring)); 22.8
(s; CH3(ring));
33.2 (s; C(CH3)2(ring));
36.8(s; C(CH3)2(bridge));
72.2 (s; CH2(bridge)); 72.3 (s; CH2(ring)); 1H NMR data (400.13 MHz;
CDCl3; 25 C): 0.77 (s; CH3(equatorial); 6H); 0.99 (s; CH3(bridge);
2
6H); 1.24 (s; CH3(axial); 6H); 3.60 (d; CH2(equatorial); 2H; JHH
=
2
11.2 Hz); 3.91 (s; CH2(bridge); 2H) 4.29 (d; CH2(axial); 2H; JHH
=
11.2 Hz).

Characterisation of Phosphorus and Arsenic Heterocyclic Compounds
2869
Synthesis of 2-Chloro 5,5-Dimethyl-1,3,2-
dioxaphosphorinane 4
To 2,2-dimethyl-1,3-propanediol (3.0 g, 28.8 mmol) neat fresh distilled
PCl3 (8 g; 58.2 mmol) was added and the mixture was stirred for 1 h.
Then the excess of PCl3 was evaporated and the product distilled under
1
reduced pressure to yield a colorless viscous oil (4.7 g, 95%). 31P{ H}
1
NMR data (81.01 MHz; CDCl3; 25 C): 145 (s); 13C{ H} NMR data
(100.61 MHz; CDCl3; 25 C): 22.3 (s; CH3); 22.4 (s; CH3); 32.8
3
2
1
(d; C(CH3)2; JCP = 4.7 Hz); 70.8 (d; CH2; JCP = 2.7 Hz); H NMR
data (400.13 MHz; CDCl3; 25 C): 0.83 (s; CH3(equatorial); 3H); 1.26
(s; CH3(axial); 3H); 3.59–3.52 (m; CH2(equatorial); 2H); 4.33–4.27
(m; CH2(axial); 2H).
Synthesis of 2-Fluoro-5,5-dimethyl-
1,3,2-dioxaphosphorinane 5
To a flask containing SbF3 (1.2 g, 6.7 mmol) 4 was added (1.1 g, 6.7 mmol)
and the mixture was stirred for 30 min. The product was distilled un-
1
der reduced pressure to yield 5 (0.7%, 71%). 31P{ H} NMR data (81.01
1
1
MHz; CDCl3; 25 C): 110 (d; JPF = 1179.7 Hz); 13C{ H} NMR data
(100.61 MHz; CDCl3; 25 C): 22.0 (s; CH3); 22.4 (d; CH3; JCF = 1.06
Hz); 32.4 (d; C(CH3)2; 3JCP = 4.83 Hz); 70.8 (dd; CH2; 2JCP = 7.62 Hz);
1H NMR data (400.13 MHz; CDCl3; 25 C): 0.78 (s; CH3(equatorial);
3H);
1.26 (s; CH3(axial); 3H);
3.47–3.39 (m; CH2(equatorial);
1
2H); 4.13–4.09 (m; CH2(axial); 2H) ; 19F{ H} NMR data (376.51 MHz;
CDCl3; 25 C): -64.9 (d; 1JPF = 1177.8 Hz).
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