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Electrophilic catalysis of N-- > 0 phosphyl migration
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Tcuahedron Letters.Vo1.32.No.1.pp 137-M. 1991 Rited in GreatBritain
ELECTROPHILIC CATALYSIS OF N-->O PHOSPHYLMIGRATION
J.Baraniak Polish
Academy of
Department
of
and W.J.Stec*
Centre
Sciences,
Bioorganic
of
Chemistry,
Molecular 90-363
and Macromolecular
Lddi,
Sienkiewicza
Studies,
112,
Poland
2-N-Benzoyl-N-phenylamino-2-oxo-5,5-dimethyl-1,3,2-dioxaphosphorinane Summary: dergoes rearrangement to (2-oxo-5,5-dimethyl-1,3,2-dioxaphosphorinanyl)(N-phenyliminobenzoyl)oxide (h). This transformation is shown to be catalysed by electrophilic such as benzoyl chloride, trimethylsilyl chloride, p-toluenesulphonyl chloride.
We originally of to
O,O-dialkyl
phosphate
that
intermediate
that
aqueous
phosphoranilidate
O,O-dialkyl
indicated
observed
the
(l) This
(2)‘.
most
work-up
in pyridine prompted
probable
course
N-benzoyl-O,O-dialkyl
of
attack
of
cisthat
and
rearrangement
system
that of
3-- >4 occurs the
this
report
phosphoranilidate we
chloride
(3)
of we
out
includes
anhydride
(4).
reaction
of
retention
3-->&
is
of
studies
were
with
stability
of
stoichiometric
between
independent
on the both
recorded
Bowever,
.
and
after
leading
[r5N1
and
5 min. the
2 h the
ppm has been
In order
4
after
intensities
ratio
interpreted
to
occurs
to
2
and
[raO]-labeled
the
to
working
evaluate
As a model
preparations
influence
of
(1)s.
appearance
key-
the
phosphoryl
of
N-benzoyl-O,O-dialkyl
of
anhydride
reaction
(6).
medium (pyridine)
of
Addi-
and benzoyl
3 and 4.
equivalent
chloride
had shown the
vely)
of
in
reaction
with (5)5.
benzoyl
chloride
in benzene (&)6.
phenyl This
gave
Independent
azide
performed
in pyridine
two products mixing of
of
signals
was ca 2:1, as characteristic
while
absorbing
2-N-benzoyl-Nstudies
reagents, at
-10.8
after for
137
intensity
and monitored
-10.8
ppm
ratio
ppm and -16.4
20 h it
on re-
(6>7
solution at
gave
compound when
2-tributylstannyloxy-2-oxo-5,5-dimethyl-l,3,2-dioxaphosphorinane
N-phenylbenzimidoyl
(spectrum
and the
2-oxo-5,5-dimethyl-1,3,2-dioxaphosphorinane.
present
studies
leads which
rearrangement
atom
undertaken.
phenylarPino-2-oxo-5,5-dimethyl-l,3,2-dioxaphosphorinane
NMR ,
a slow
we formulated
by pyridine.
2-Methoxy-5,5-dimethyl-1,3,2-dioxaphosphorinane4
action
chloride
we established
configuration;
catalysed
treatment
studies,
Hydrolysis
N-phenylimino-carbon of
benzoyl
N-benzoylation,
undergoes
2-methoxy-2-N-phenylimino-5,5-dimethyl-l,3,2-dioxaphosphorinane treated
of
un-
reagents
from
more detailed
and O,O-dialkylphosphoric-N-phenyliminobenzoic
present
on the
with
more detailed
derivatives
this
tionally
at
an excess
(2)
zrP NMR studies
rearrangement
hypothesis
we chose In
of
mixture
trans-2-N-phenylamino-2-oxo-4-methyl-l,3,2-dioxaphosphorinanes3
hypothesis validity
basis
reaction
carry
events
mixed
exclusively
water On the
benzanilidatez.
the
with
us to
phosphoranilidate
O,O-dialkylphosphoric-N-phenyliminobenzoic with
of
(&)
and
was ca.l:4, ppm were
was ca 4:l.
time
The signal
(5,5-dimethyl-1,3,2-dioxaphosphorinyi)(N-
and
by 3rP
-16.4
ppm
respectidependent at
-16.4
138
phenyliminobenzoyl)oxide which
to a, Similarly, (6)
condensation
with
of
a similar
mixing
of
These the
reagents,
results
chloride
appearing
of
and 5:l
sence
of
after
stable
proved
(-10.8
20 h, that
of
bond
was
proved
the
products
0-->N
phosphyl
as corresponding to
the
NMR tube.
of
the
reaction
under
slow
rearrangement
between
pattern
Higher
I:2
one
hr
thermodynamic
condensation
of
since
indicating
stability
of
the
of
dialkyl
This
l_a.
chloride,
in Fig.1,
earlier,results
conditions,
to
2-tributylstannyloxy-2-oxo-
3a under
with
had shown in
ratio
and [15N]N-phenylbenzimidoyl splitting
in a.
consistent
solution, ppm,
respectively).
condensation
(5)
conditions
undergoes
&
in pyridine
phenylamino-2-oxo-5,5-dimethyl-l,3,2-dioxaphosphorinane
primary
of
ppm and -16.4
and undergoes
ppm showed the
perimental that
sample
compound 4a is,
product
by results
rsN-3rP
direct
was recognized
a genuine
performed
signals
indicated
less
at -10.8
of
(Z),
5,5-dimethyl-1,3,2-dioxaphosphorinane signal
one at -10.8ppm
2-trimethylsilyloxy-2-oxo-5,5-dimethyl-1,3,2-dioxaphosphorinane
clearly
unambiguously
the
by addition
pattern
thermodynamically
was
while
N-phenylbenzimidoyl
srP NMR assay after
(&),
has been confirmed
the
the
pre-
2-N-behzoyl-N-
aforementioned
Mikolajczyk
phosphorothioic
ex-
et.al.lO,
who
acid
DCC
with
migration. Figure
I
slP MNR spectrum
1.
mixture
between
of
the
reaction
2-tributylstannyloxy
-2-
oxo-5,5-dimethyl-1,3,2-dioxaphosphorinane (61) and [lSNIN-phenylbenzimidoyl 6 -9 3a -9
.I..,
.I,.,
prompted
anhydrides excess
of
showed
4.
This
is
caused
after
96 h only
oxygen
an excess
for of
chloride.
in the
text
the
intramolecular
benzoyl
chloride
as well
benzoyl
signal
of at
that
-16.4
on
the
equal
-10.8
results the
presented
stability
phosphyl
benzoyl
11 h after
migration
deficit
by the carbonyl the
stability
vide of
N-
with
an
is
of
characteristic
(rearrangement
at phosphorus
structure
reagents.
ppm and -16.4
and presumably
oxygen. of
mixing
at -10.8 which
chloride,
electron
ppm) was treated
intensities
ppm was present,
N--Xl
increasing
(631P recorded
nearly
of
increases
chloride
solution
assistance
attack
as the
and O,O-dialkylphosphoric-N-phenyliminobenzoic
31P NMR spectra,
proved
involvement,
of (2)
in pyridine
the
w
-I?.@
reports”,
influence
two signals
of
unambiguously
more susceptive of
when &
by the electrophilic
phosphoryl
.,..a
previous
the
chloride,
presence
result
study
However,
benzoyl
ppm, while
ail
phosphoranilidates
(4).
the
of
us to
.,,.a
.I..0
analysis
benzoyl-O,O-dialkyl
explained
*
.u..
.I,.#
Careful supra,
c
0
IL1
&X are
&g--a&) occurs
and making
Moreover, 4 (Scheme
of
the 1).
via it
presence
139
0
0 :h-NPh
+ Ph[C\
-
O=tPh 1
1 CL:;-O-C=
+
NPh
PhiCl
PhC-O-,b
-
.k
‘O-CPh
Phi
bh
I;
I
_
Scheme 1.
Electrophilic methylsilyl
chloride
disappearance
of & and
other than benzoyl
resulting the
of
by
independent
If &a was treated
rearrangement to h.
reversed
from reaction
formation
has been proven
chloride.
it underwent complete by vacuum evaporation
Treatment of b,
phorinane
in the rearrangement J-+4
electrophiles
chloride/pyridine,
of trimethylsilyl 4-->3).
assistance
with
experiments
the
However, removal
process,
& and MesSiCl/Py,
with tri-
(rearrangement
with water,
caused
2-hydroxy-2-oxo-5,5-dimethyl-1,3,2-dioxaphos-
(&)ls.
0
K
0
;kfQCH3
,B
&-
G,P-NPhCPh
t7
0 G$-OtPh
& -1
-3a
Scheme
2 : il tlc3SiCL
; iil@PIOICI
NPh
-Ca
; iiil(PhO)2PlOlCI;
iv1CH30qC1 The provide
results
presented
strong evidence
methylsilyl arrangement.
chloride
on electrophilic
for covalent
assistance
electrophilic
can be removed by evaporation,
However, when a
pyridine
solution
in the rearrangement a-->& do not
catalysis, which results
of Jp was treated
since
the
volatile
in the reverse
tri-
&-->a re-
with 2-chloro-2-oxo-5,5-
140
(9) 1s
dimethyl-1,3,2-dioxaphosphorinane sylnmetrical (u)ra
pyrophosphate,
(Scheme
unsymmetrical phenyl
namely
while
similar
pyrophosphate,
phosphoryl)oxide
Analogous the
2),
reaction
appearance
of
mixed
with
by
addition
of
2
phosphoric-sulphonic
These
results
chloride, mation
of
a genuine
strengthen
the
of
structures
benzoyl-O,O-dialkyl indicate
of
(3)
of
the
gave
ppm,
2J=19.2
Hz).
ppm);
according
of
10,
chloride
led
to
its
identity
to Michalski assistance
3-->$
is
rearrangement
a1.r4.
(phosphoryl
rearrangement,
12 and u
was
et
since
possible
only
to anhydride
4,
forif
N-
but
also
4.
in this
indebted
(11)
(5,5-dimethyl-2-oxo-1,3,2-
-20.3
electrophilic
process
undergoes
of
namely
prepared
in compounds
reported
are
12,
in the
properties
Studies Authors
phosphorochloridate
ppm and -23.16
831P
concerning
phosphoranilidate
Acknowledgment: CPBR 3.13.4.
sample
as these
the phosphorylating
appearance
p-toluenesulphonyl
anhydride,
chloride)
such
with
(12,
hypothesis
p-toluenesulphonyl
O,O-diphenyl
at 631P -20.8
solution
dioxaphosphorinanyl)(p-toluenesulphonyl)oxide proved
showed the
(2-oxo-5,5-dimethyl-1,3,2-dioxaphosphorinanyl)(O,O-di-
two doublets
a pyridine
arP NMR control
bis(2-oxo-5,5-dimethyl-1,3,2-dioxaphosphorinanyl)oxide
treatment
namely
(12,
of
the
paper
were
financially
E.Wasilewska
to Ms.
for
assisted
by the
her excellent
technical
project assis-
tance.
References: 1.
J.Baraniak,
2.
J.Baraniak.
3.
W.J.Stec,
4.
R.S.Edmundson; yield
K.Lesiak,
W.J.Stec;
W.J.Stec;
Phosphorus
A.Lopusiriski;
5.
5: &:
63%; n.p.
7.
Compound 6 had been
yield
tion
B,
2781
obtained
1387 (1979).
29,
115 (1986).
547 (1973).
(1964).
MS(70eV)
137-159OC;
53,
m/z 255(M+,80%),
MS(70eV)
187(100%);
m/z 345(M+,20%),
according
to
procedure
631P -9.0
105(100X);
described
in methylene
and had been used
chloride
without
at
by Hata et
any purification
after
ppm (CDCls).
al.*,
in
and
This
room temperature.
ppm(CDCla).
631P -9.4
2-hydroxy-2-oxo-5,5-dimethyl-1,3,2-dioxaphosphorinane
between
methoxide
a,
99-10l°C;
52%; m.p.
and Sulfur
Tetrahedron
Tetrahedron
6.
Pol.J.Chem.
complete
compound
removal
of
is
the
reac-
tri-n-butyltin
a white
solvent,
sticky
solid
631P -9.9
ppm
(C5H5N). 8.
K.Yanaguchi,
9.
N-Phenylbenziaidoyl
10.
M.Mikolajczyk,
thionyl
T.Kamimura,
chloride.
T.Hata;
chloride Yield
89%. m.p.
that
been 40-41°C,
A.Sut;
P.Kielbasidski,
11. Modro had reported
J.Am.Chem.Soc. had
b.p.
4534 in
62.
(1980).
the
175OC/12
Tetrahedron
reaction
anhydrides
between
V.Mierahi,
13.
R.S.Edmundson;
T.A.Modro;
14.
W.Dabkowski,
J.Org.Chem.
Tetrahedron Z.Skrxypcxydski,
(Received in UK 2 November 19!IO)
21,
42,
2379
3533
undergo
under
condition
of
rearrengement electron
(1982).
(1965).
J.Hichalski;
Nucl.Acids
and
(1986).
(70eV,2C0°C)1*.
12.
benzanilide
mm Hg.
4591
N-benzoyl-O,O-dialkyl‘phosphoramidates
dialkylphosphoric-N-phenyliminocarboxylic spectrometer
102,
obtained
Res.
u,
9123
(1984).
to O,O-
impact
mass
Tcuahedron Letters.Vo1.32.No.1.pp 137-M. 1991 Rited in GreatBritain
ELECTROPHILIC CATALYSIS OF N-->O PHOSPHYLMIGRATION
J.Baraniak Polish
Academy of
Department
of
and W.J.Stec*
Centre
Sciences,
Bioorganic
of
Chemistry,
Molecular 90-363
and Macromolecular
Lddi,
Sienkiewicza
Studies,
112,
Poland
2-N-Benzoyl-N-phenylamino-2-oxo-5,5-dimethyl-1,3,2-dioxaphosphorinane Summary: dergoes rearrangement to (2-oxo-5,5-dimethyl-1,3,2-dioxaphosphorinanyl)(N-phenyliminobenzoyl)oxide (h). This transformation is shown to be catalysed by electrophilic such as benzoyl chloride, trimethylsilyl chloride, p-toluenesulphonyl chloride.
We originally of to
O,O-dialkyl
phosphate
that
intermediate
that
aqueous
phosphoranilidate
O,O-dialkyl
indicated
observed
the
(l) This
(2)‘.
most
work-up
in pyridine prompted
probable
course
N-benzoyl-O,O-dialkyl
of
attack
of
cisthat
and
rearrangement
system
that of
3-- >4 occurs the
this
report
phosphoranilidate we
chloride
(3)
of we
out
includes
anhydride
(4).
reaction
of
retention
3-->&
is
of
studies
were
with
stability
of
stoichiometric
between
independent
on the both
recorded
Bowever,
.
and
after
leading
[r5N1
and
5 min. the
2 h the
ppm has been
In order
4
after
intensities
ratio
interpreted
to
occurs
to
2
and
[raO]-labeled
the
to
working
evaluate
As a model
preparations
influence
of
(1)s.
appearance
key-
the
phosphoryl
of
N-benzoyl-O,O-dialkyl
of
anhydride
reaction
(6).
medium (pyridine)
of
Addi-
and benzoyl
3 and 4.
equivalent
chloride
had shown the
vely)
of
in
reaction
with (5)5.
benzoyl
chloride
in benzene (&)6.
phenyl This
gave
Independent
azide
performed
in pyridine
two products mixing of
of
signals
was ca 2:1, as characteristic
while
absorbing
2-N-benzoyl-Nstudies
reagents, at
-10.8
after for
137
intensity
and monitored
-10.8
ppm
ratio
ppm and -16.4
20 h it
on re-
(6>7
solution at
gave
compound when
2-tributylstannyloxy-2-oxo-5,5-dimethyl-l,3,2-dioxaphosphorinane
N-phenylbenzimidoyl
(spectrum
and the
2-oxo-5,5-dimethyl-1,3,2-dioxaphosphorinane.
present
studies
leads which
rearrangement
atom
undertaken.
phenylarPino-2-oxo-5,5-dimethyl-l,3,2-dioxaphosphorinane
NMR ,
a slow
we formulated
by pyridine.
2-Methoxy-5,5-dimethyl-1,3,2-dioxaphosphorinane4
action
chloride
we established
configuration;
catalysed
treatment
studies,
Hydrolysis
N-phenylimino-carbon of
benzoyl
N-benzoylation,
undergoes
2-methoxy-2-N-phenylimino-5,5-dimethyl-l,3,2-dioxaphosphorinane treated
of
un-
reagents
from
more detailed
and O,O-dialkylphosphoric-N-phenyliminobenzoic
present
on the
with
more detailed
derivatives
this
tionally
at
an excess
(2)
zrP NMR studies
rearrangement
hypothesis
we chose In
of
mixture
trans-2-N-phenylamino-2-oxo-4-methyl-l,3,2-dioxaphosphorinanes3
hypothesis validity
basis
reaction
carry
events
mixed
exclusively
water On the
benzanilidatez.
the
with
us to
phosphoranilidate
O,O-dialkylphosphoric-N-phenyliminobenzoic with
of
(&)
and
was ca.l:4, ppm were
was ca 4:l.
time
The signal
(5,5-dimethyl-1,3,2-dioxaphosphorinyi)(N-
and
by 3rP
-16.4
ppm
respectidependent at
-16.4
138
phenyliminobenzoyl)oxide which
to a, Similarly, (6)
condensation
with
of
a similar
mixing
of
These the
reagents,
results
chloride
appearing
of
and 5:l
sence
of
after
stable
proved
(-10.8
20 h, that
of
bond
was
proved
the
products
0-->N
phosphyl
as corresponding to
the
NMR tube.
of
the
reaction
under
slow
rearrangement
between
pattern
Higher
I:2
one
hr
thermodynamic
condensation
of
since
indicating
stability
of
the
of
dialkyl
This
l_a.
chloride,
in Fig.1,
earlier,results
conditions,
to
2-tributylstannyloxy-2-oxo-
3a under
with
had shown in
ratio
and [15N]N-phenylbenzimidoyl splitting
in a.
consistent
solution, ppm,
respectively).
condensation
(5)
conditions
undergoes
&
in pyridine
phenylamino-2-oxo-5,5-dimethyl-l,3,2-dioxaphosphorinane
primary
of
ppm and -16.4
and undergoes
ppm showed the
perimental that
sample
compound 4a is,
product
by results
rsN-3rP
direct
was recognized
a genuine
performed
signals
indicated
less
at -10.8
of
(Z),
5,5-dimethyl-1,3,2-dioxaphosphorinane signal
one at -10.8ppm
2-trimethylsilyloxy-2-oxo-5,5-dimethyl-1,3,2-dioxaphosphorinane
clearly
unambiguously
the
by addition
pattern
thermodynamically
was
while
N-phenylbenzimidoyl
srP NMR assay after
(&),
has been confirmed
the
the
pre-
2-N-behzoyl-N-
aforementioned
Mikolajczyk
phosphorothioic
ex-
et.al.lO,
who
acid
DCC
with
migration. Figure
I
slP MNR spectrum
1.
mixture
between
of
the
reaction
2-tributylstannyloxy
-2-
oxo-5,5-dimethyl-1,3,2-dioxaphosphorinane (61) and [lSNIN-phenylbenzimidoyl 6 -9 3a -9
.I..,
.I,.,
prompted
anhydrides excess
of
showed
4.
This
is
caused
after
96 h only
oxygen
an excess
for of
chloride.
in the
text
the
intramolecular
benzoyl
chloride
as well
benzoyl
signal
of at
that
-16.4
on
the
equal
-10.8
results the
presented
stability
phosphyl
benzoyl
11 h after
migration
deficit
by the carbonyl the
stability
vide of
N-
with
an
is
of
characteristic
(rearrangement
at phosphorus
structure
reagents.
ppm and -16.4
and presumably
oxygen. of
mixing
at -10.8 which
chloride,
electron
ppm) was treated
intensities
ppm was present,
N--Xl
increasing
(631P recorded
nearly
of
increases
chloride
solution
assistance
attack
as the
and O,O-dialkylphosphoric-N-phenyliminobenzoic
31P NMR spectra,
proved
involvement,
of (2)
in pyridine
the
w
-I?.@
reports”,
influence
two signals
of
unambiguously
more susceptive of
when &
by the electrophilic
phosphoryl
.,..a
previous
the
chloride,
presence
result
study
However,
benzoyl
ppm, while
ail
phosphoranilidates
(4).
the
of
us to
.,,.a
.I..0
analysis
benzoyl-O,O-dialkyl
explained
*
.u..
.I,.#
Careful supra,
c
0
IL1
&X are
&g--a&) occurs
and making
Moreover, 4 (Scheme
of
the 1).
via it
presence
139
0
0 :h-NPh
+ Ph[C\
-
O=tPh 1
1 CL:;-O-C=
+
NPh
PhiCl
PhC-O-,b
-
.k
‘O-CPh
Phi
bh
I;
I
_
Scheme 1.
Electrophilic methylsilyl
chloride
disappearance
of & and
other than benzoyl
resulting the
of
by
independent
If &a was treated
rearrangement to h.
reversed
from reaction
formation
has been proven
chloride.
it underwent complete by vacuum evaporation
Treatment of b,
phorinane
in the rearrangement J-+4
electrophiles
chloride/pyridine,
of trimethylsilyl 4-->3).
assistance
with
experiments
the
However, removal
process,
& and MesSiCl/Py,
with tri-
(rearrangement
with water,
caused
2-hydroxy-2-oxo-5,5-dimethyl-1,3,2-dioxaphos-
(&)ls.
0
K
0
;kfQCH3
,B
&-
G,P-NPhCPh
t7
0 G$-OtPh
& -1
-3a
Scheme
2 : il tlc3SiCL
; iil@PIOICI
NPh
-Ca
; iiil(PhO)2PlOlCI;
iv1CH30qC1 The provide
results
presented
strong evidence
methylsilyl arrangement.
chloride
on electrophilic
for covalent
assistance
electrophilic
can be removed by evaporation,
However, when a
pyridine
solution
in the rearrangement a-->& do not
catalysis, which results
of Jp was treated
since
the
volatile
in the reverse
tri-
&-->a re-
with 2-chloro-2-oxo-5,5-
140
(9) 1s
dimethyl-1,3,2-dioxaphosphorinane sylnmetrical (u)ra
pyrophosphate,
(Scheme
unsymmetrical phenyl
namely
while
similar
pyrophosphate,
phosphoryl)oxide
Analogous the
2),
reaction
appearance
of
mixed
with
by
addition
of
2
phosphoric-sulphonic
These
results
chloride, mation
of
a genuine
strengthen
the
of
structures
benzoyl-O,O-dialkyl indicate
of
(3)
of
the
gave
ppm,
2J=19.2
Hz).
ppm);
according
of
10,
chloride
led
to
its
identity
to Michalski assistance
3-->$
is
rearrangement
a1.r4.
(phosphoryl
rearrangement,
12 and u
was
et
since
possible
only
to anhydride
4,
forif
N-
but
also
4.
in this
indebted
(11)
(5,5-dimethyl-2-oxo-1,3,2-
-20.3
electrophilic
process
undergoes
of
namely
prepared
in compounds
reported
are
12,
in the
properties
Studies Authors
phosphorochloridate
ppm and -23.16
831P
concerning
phosphoranilidate
Acknowledgment: CPBR 3.13.4.
sample
as these
the phosphorylating
appearance
p-toluenesulphonyl
anhydride,
chloride)
such
with
(12,
hypothesis
p-toluenesulphonyl
O,O-diphenyl
at 631P -20.8
solution
dioxaphosphorinanyl)(p-toluenesulphonyl)oxide proved
showed the
(2-oxo-5,5-dimethyl-1,3,2-dioxaphosphorinanyl)(O,O-di-
two doublets
a pyridine
arP NMR control
bis(2-oxo-5,5-dimethyl-1,3,2-dioxaphosphorinanyl)oxide
treatment
namely
(12,
of
the
paper
were
financially
E.Wasilewska
to Ms.
for
assisted
by the
her excellent
technical
project assis-
tance.
References: 1.
J.Baraniak,
2.
J.Baraniak.
3.
W.J.Stec,
4.
R.S.Edmundson; yield
K.Lesiak,
W.J.Stec;
W.J.Stec;
Phosphorus
A.Lopusiriski;
5.
5: &:
63%; n.p.
7.
Compound 6 had been
yield
tion
B,
2781
obtained
1387 (1979).
29,
115 (1986).
547 (1973).
(1964).
MS(70eV)
137-159OC;
53,
m/z 255(M+,80%),
MS(70eV)
187(100%);
m/z 345(M+,20%),
according
to
procedure
631P -9.0
105(100X);
described
in methylene
and had been used
chloride
without
at
by Hata et
any purification
after
ppm (CDCls).
al.*,
in
and
This
room temperature.
ppm(CDCla).
631P -9.4
2-hydroxy-2-oxo-5,5-dimethyl-1,3,2-dioxaphosphorinane
between
methoxide
a,
99-10l°C;
52%; m.p.
and Sulfur
Tetrahedron
Tetrahedron
6.
Pol.J.Chem.
complete
compound
removal
of
is
the
reac-
tri-n-butyltin
a white
solvent,
sticky
solid
631P -9.9
ppm
(C5H5N). 8.
K.Yanaguchi,
9.
N-Phenylbenziaidoyl
10.
M.Mikolajczyk,
thionyl
T.Kamimura,
chloride.
T.Hata;
chloride Yield
89%. m.p.
that
been 40-41°C,
A.Sut;
P.Kielbasidski,
11. Modro had reported
J.Am.Chem.Soc. had
b.p.
4534 in
62.
(1980).
the
175OC/12
Tetrahedron
reaction
anhydrides
between
V.Mierahi,
13.
R.S.Edmundson;
T.A.Modro;
14.
W.Dabkowski,
J.Org.Chem.
Tetrahedron Z.Skrxypcxydski,
(Received in UK 2 November 19!IO)
21,
42,
2379
3533
undergo
under
condition
of
rearrengement electron
(1982).
(1965).
J.Hichalski;
Nucl.Acids
and
(1986).
(70eV,2C0°C)1*.
12.
benzanilide
mm Hg.
4591
N-benzoyl-O,O-dialkyl‘phosphoramidates
dialkylphosphoric-N-phenyliminocarboxylic spectrometer
102,
obtained
Res.
u,
9123
(1984).
to O,O-
impact
mass