N→C2→C3 migration of the dichlorophosphino group in the synthesis of phosphorylated NH-pyrroles

Article abstract of DOI:10.1002/hc.20495

A successive N→C₂→C₃ migration of the dichlorophosphino group has been found to occur in phosphorylation of unsubstituted pyrrole with phosphorus trichloride. As a result of this migration, a number of hitherto unknown C-phosphorylated N-unsubstituted pyrroles have been obtained.

Full text of DOI:10.1002/hc.20495

Heteroatom Chemistry
Volume 19, Number 7, 2008
N→ C → C Migration of the
2
3
Dichlorophosphino Group in the Synthesis
of Phosphorylated NH-Pyrroles
Aleksandra A. Chaikovskaya,1 Yurii V. Dmytriv,1
Nadiya V. Shevchuk,1 Radomyr V. Smaliy,1
Aleksander M. Pinchuk,1 and Andrey A. Tolmachev2
1Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Murmanska St. 5,
Kyiv-94, 02094, Ukraine
2Research and Development Center for Chemistry and Biology, National Taras Shevchenko
University, Volodymyrska St. 62, Kyiv-33, 01033, Ukraine
Received 1 April 2008; revised 14 July 2008
[3–7], as well as the reactions of 2,4-dimethylpyrroles
ABSTRACT:
A
successive N → C2 → C3 migra-
and 2,3,5-trimethylpyrroles with chlorophosphites
that occur nonselectively at the pyrrole NH group
and the C2 and C3 atoms [8]. Several N → C2 and
C2 → C3 migrations of electrophilic groups (C O,
SO2, P O, and PBr2) in pyrroles are also known [9–
12].
It looks plausible that the successive
N → C2 → C3 migration of phosphino groups
takes place in phosphorylation of the unsubstituted
pyrrole with phosphorus(III) halides. Moreover, a
rearrangement of this kind could directly lead to
3-phosphorylated pyrroles, which bear an unsub-
stituted NH functionality [13] capable of further
reactions.
tion of the dichlorophosphino group has been
found to occur in phosphorylation of unsubsti-
tuted pyrrole with phosphorus trichloride. As a re-
sult of this migration, a number of hitherto un-
known C-phosphorylated N-unsubstituted pyrroles
ꢀ
C
have been obtained.
2008 Wiley Periodicals, Inc.
Heteroatom Chem 19:671–676, 2008; Published online
in Wiley InterScience (www.interscience.wiley.com). DOI
10.1002/hc.20495
INTRODUCTION
The literature lacks studies on the phosphoryla-
tion of unsubstituted pyrrole, whereas studies on
halogenophosphines are scarce. Some evidence was
reported for the reactions of potassium pyrrolide
[1] and pyrrole in the presence of a base [2]
with chlorophosphines, involving a pyrrole nitrogen
atom, N-pyrrolylmagnesium bromide with phospho-
rus halides affording C2-phosphorylated derivatives
RESULTS AND DISCUSSION
As found, phosphorylation of pyrrole
1 with
phosphorus trichloride in dichloromethane in the
presence of a base (1 mol of triethylamine or
pyridine) proceeds via the following pathway: An
initially formed N-phosphorylated intermediate, N-
pyrrolyldichlorophosphine 2, undergoes the N → C2
migration of the dichlorophosphino group in a mat-
ter of hours to give 2-pyrrolyldichlorophosphine
3 in which the C2 → C3 migration of the same
Correspondence to: Aleksandra A. Chaikovskaya; e-mail:
chaikoff2005@ukr.net.
c
ꢀ
2008 Wiley Periodicals, Inc.
671

672 Chaikovskaya et al.
group occurs in a period of 3–5 days, leading to
3-pyrrolyldichlorophosphine 4. Thus, we have re-
vealed a successive N → C2 → C3 migration of the
dichlorophosphino group in the pyrrole.
polar benzene, the rearrangement is slowed down
significantly and requires 1 month to go to comple-
tion. Although in chloroform the migration rate is
almost the same as in dichloromethane, but many
PCl2
PCl
3 ,Py
N
H
CH2Cl2
PCl2
N
N
H
N
H
PCl2
4
1
3
2
H
H
N
H
N
N
X
O
O
O
N
O
P
X
2
P
N
X
N
N
N
N
H
O
P
N
H
P
N
X
2
8
7 a,b
O
O
2
2
a: X=O
b: X=S
5
6a,b
a: X=O
b: X=S
31P NMR monitoring of the reaction between
pyrrole 1 and phosphorus trichloride in the pres-
ence of triethylamine demonstrates that the signals
of the N-phosphorylated intermediate 2 (148.4 ppm),
2-pyrrolyldichlorophosphine 3 (132.7 ppm), and 3-
pyrrolyldichlorophosphine 4 (158.7 ppm) appear
within 1, 2, and 5 h, respectively, after mixing the
reagents. The signal of compound 4 is progressively
enhanced and becomes a single one 5 days later. The
rearrangement concerned is much accelerated if the
reaction is conducted in the presence of pyridine.
In this case, only trace amounts of the initial com-
pound 2 can be detected by 31P NMR spectroscopy,
whereas 3 becomes the main product already after
1 h of reaction time and it is completely converted
to 4 within 4 days.
by-products are formed. We failed to carry out the
N → C2 → C3 migration of the dichlorophosphino
group in pyridine. A number of unidentified signals
were observed in the 31P NMR spectrum of the reac-
tion mixture.
We failed to isolate pyrrolyldichlorophosphines
2, 3, and 4 in the pure state because any isola-
tion procedures caused polymerization of products.
Two phosphorus(III) compounds, amides 5 and 8,
were isolated in the pure state; their structures were
1
supported by H, 13C, and 31P NMR spectra as well
as by elemental analysis and high performance liq-
uid chromatography. For unequivocal structural de-
termination of products 2–4, they were converted
to stable phosphorus(V) compounds 6a,b, 7a,b,
9–12, and phosphonium salt 13. The phosphorus
atom position in products 5, 6a,b, 7a,b, and 8–13
was firmly established by 1H, 13C, and 31P NMR
spectra.
It should also be noted that the nature of
the solvent influences the migration rate of the
dichlorophosphino group in the pyrrole ring. In non-
Heteroatom Chemistry DOI 10.1002/hc

N → C2 → C3 Migration of the Dichlorophosphino Group in the Synthesis of Phosphorylated NH-Pyrroles 673
S
P
O
N
S
2
N
H
9
O
CH3
P
N
O
O
Cl3C-CCl3
NaHCO3
2
CH3
O
8
N
10
H
N
N
N
N
P
H3C
O
P
O
N
N
O
N3
2
2
−N2
N
N
H
H
11
12
CH3I
+
P
−
H3C
N
O
I
2
N
H
13
As shown previously, the C2 → C3 migra-
tion of the dibromophosphino group in the N-
methylpyrrole ring is catalyzed by pyridine hydro-
bromide [11]. We have also observed the effect
of acidic impurities on the N → C2 → C3 migration
of the dichlorophosphino group. If the reaction is
run with freshly distilled phosphorus trichloride in
deacidified dichloromethane, the migration rate is
strongly reduced. Thus, the rearrangement is prob-
ably facilitated by hydrogen chloride present in the
reaction mixture:
pyrrole 1 with excess (3 eq.) phosphorus trichloride,
only one dichlorophosphino group is introduced
into the pyrrole nucleus and its N → C2 → C3 migra-
tion proceeds in a normal manner, as demonstrated
above. It is also notable that N-phosphorylated
pyrroles 6 a,b could not be phosphorylated further
even in pyridine with phosphorus tribromide, the
most reactive phosphorylating agent.
We have also studied the action of phosphorus
trichloride on 2,5-dimethylpyrrole 14. In this case,
the phosphorus atom directly attacks the C3 atom
of the pyrrole ring. Accordingly, the 31P NMR spec-
tra show no trace of the signal of the N-substituted
product immediately after starting the reaction; in-
stead, a signal at 158.5 ppm is observed that cor-
responds to 3-pyrrolyldichlorophosphine 15. This
∗
−→
←−
Et3N HCl
Et3N + HCl
These results suggest the following scheme for the
N → C2 → C3 migration of the dichlorophosphino
group:
PCl2
Et3N
HCl
Et3N
HCl
PCl
+
PCl
3
+
3
N
Et3N
PCl2
HCl
HCl
Et3N
N
H
N
H
N
H
N
H
PCl2
reaction course is attributable to steric constraints
at the nitrogen atom caused by two methyl groups;
it may also result from the fact that the C3 atom of
Attempted direct phosphorylation of pyrrole 1
with phosphorus tribromide resulted in the forma-
tion of polymeric products. On phosphorylation of
Heteroatom Chemistry DOI 10.1002/hc

674 Chaikovskaya et al.
the pyrrole ring is the most nucleophilic center in
compound 16.
O
PCl2
N
O
P
O
H
N
H O
,
2 2
4
PCl3, Py
2
H3C
CH3
N
H
H3C
CH3
CH2Cl2
N
H
H3C
CH3
N
H
14
15
16
CONCLUSION
1H-Pyrrol-1-yl[di(4-morpholyl)]phosphine
Oxide 6a
The study on direct phosphorylation of N-
unsubstituted pyrrole with phosphorus trichloride
has revealed that the reaction involves a successive
N → C2 → C3 migration of the dichlorophosphino
group. As a result of the rearrangement found, a
number of hitherto unknown C-phosphorylated NH-
pyrroles have been obtained.
To a stirred solution of amide 5 (0.01 mol) in benzene
(30 mL), 50% H2O2 (0.03 mol) was added at room
temperature. The reaction mixture was stirred for
1 h and then diluted with H2O (10 mL). The organic
layer was separated, dried over Na2SO4, and evapo-
rated. Product 6a was isolated as a light-colored oil.
Yield 42%. 31P NMR (CDCl3): δ 9.9. 1H NMR (CDCl3):
δ 3.00 (m, 8H, O CH2), 3.49 (m, 8H, N-CH2), 6.26
(br s, 2H, H3,4), 6.99 (br s, 2H, H2,5). m/z = 286 [M]+.
Anal. Calcd. for C12H20N3O3P (285): C 50.52, H 7.07,
N 14.73. Found: C 50.50, H 7.09, N 14.70.
EXPERIMENTAL
1H, 13C, and 31P NMR spectra were recorded on a
Varian VXR-300 spectrometer (at 300, 75, and 121
MHz, respectively, 25◦C), with TMS as internal stan-
dard for 1H and 13C signals, and 85% H3PO4 as exter-
nal standard for 31P signals. Liquid chromatography
mass spectra were registered on an Agilent 1100 Se-
ries LC/MSD instrument.
1H-Pyrrol-1-yl[di(4-morpholyl)]phosphine
Sulfide 6b
To a stirred solution of amide 5 (0.01 mol) in benzene
(30 mL), elementary sulfur (0.01 mol) was added,
followed by boiling the reaction mixture for 30 min.
After evaporating the reaction mixture, the residue
was treated with diethyl ether. The resulting pre-
cipitate was filtered off and recrystallized from di-
ethyl ether. Yield 83%. 31P NMR (DMSO-d6): δ 64.4.
1H NMR (DMSO-d6): δ 3.02 (m, 8H, O CH2), 3.53
(m, 8H, N-CH2), 6.33 (br s, 2H, H3,4), 7.16 (br s, 2H,
H2,5).13C NMR (DMSO-d6): δ 45.95 (s, O CH2), 66.74
(s, N-CH2), 112.65 (d, JCP = 9.0 Hz, C3,4), 123.56
(d, JCP = 4.0 Hz, C2,5) m/z = 302 [M]+. Anal. Calcd
for C12H20N3O2PS (301): C 47.83, H 6.69, N 13.94.
Found: C 47.81, H 6.67, N 13.91.
1H-Pyrrol-1-yl[di(4-morpholyl)]phosphine 5
To an ice-cooled and stirred solution of pyrrole
1 (0.01 mol) and pyridine (0.01 mol) in CH2Cl2
(60 mL), PCl3 (0.01 mol) was added under dry ar-
gon. The reaction mixture was allowed to stand at
room temperature for 1 h (until a 31P NMR signal at
148.4 ppm was detected), followed by adding pen-
tane (100 mL), cooling to 0◦C, and decanting the
pentane layer thrice under argon. To the residue dis-
solved in benzene, morpholine (0.05 mol) was added
with ice-cooling and stirring. The reaction mixture
was stirred at room temperature for 2 h, the precipi-
tate of morpholine hydrochloride was filtered off un-
der argon, and the filtrate was evaporated. Product
5 was isolated as a light-colored oil. Yield 78%. 31P
1H-Pyrrol-2-yl[di(4-morpholyl)]phosphine
Oxide 7a
1
NMR (CDCl3): δ 105.9. H NMR (CDCl3): δ 3.05 (m,
To an ice-cooled and stirred solution of pyrrole
1 (0.01 mol) and pyridine (0.01 mol) in CH2Cl2
(60 mL), PCl3 (0.01 mol) was added under dry ar-
gon. The reaction mixture was allowed to stand at
room temperature for 2.5 h (until a 31P NMR signal
8H, N-CH2), 3.63 (m, 8H, O CH2), 6.30 (s, 2H, H3,4),
6.88 (s, 2H, H2,5). m/z = 270 [M]+. Anal. Calcd for
C12H20N3O2P (269): C 53.52, H 7.49, N 15.60. Found:
C 53.50, H 7.46, N 15.57.
Heteroatom Chemistry DOI 10.1002/hc

N → C2 → C3 Migration of the Dichlorophosphino Group in the Synthesis of Phosphorylated NH-Pyrroles 675
at 132.7 ppm was detected), followed by adding pen-
the residue in benzene and cooling the solution with
ice, morpholine (0.05 mol) was added with stirring.
The reaction mixture was allowed to stand for 1 h
(until the 31P NMR signal at 89.5 ppm appeared),
and filtered to remove the precipitate of morpho-
line hydrochloride. The filtrate was evaporated and
kept in vacuum. The product was isolated as a light-
colored oil. Yield 85%. 31P NMR (DMSO-d6): δ 87.5.
1H NMR (CDCl3): δ 3.01 (m, 8H, O CH2), 3.57 (m,
8H, N-CH2), 6.06 (br s, 1H, H4), 6.72 (br s, 1H, H2),
9.79 (br s, 1H, NH). m/z 270 [M]+. Anal. Calcd for
C12H20N3O2P (269): C 53.52, H 7.49, N 15.60. Found:
C 53.51, H 7.48, N 15.59.
tane (100 mL), cooling to 0◦C, and decanting the
pentane layer thrice under argon. To the residue
dissolved in benzene, morpholine (0.05 mol) was
added with ice cooling and stirring. After 1 h of
standing (when the 31P NMR signal at 85.6 ppm
appeared), the reaction mixture was filtered to re-
move the precipitate of morpholine hydrochloride.
Hexachloroethane (0.01 mol) was added to the fil-
trate, and the mixture was left overnight. The re-
sulting phosphonium salt precipitate was filtered
off, washed with benzene, and dissolved in CH2Cl2
(50 mL). After shaking the solution with 20% aque-
ous NaHCO3, the organic layer was separated, dried
over Na2SO4, and evaporated. The product was re-
crystallized from diethyl ether. Yield 55%. mp 190–
192◦C. 31P NMR (DMSO-d6): δ 11.0. 1H NMR (DMSO-
d6): δ 2.96 (m, 8H, O CH2), 3.56 (m, 8H, N-CH2), 6.10
(br s, 1H, H4), 6.56 (br s, 1H, H3), 6.99 (br s, 1H, H5),
11.63 (br s, 1H, NH).13C NMR (DMSO-d6): δ 44.09 (s,
O CH2), 66.14 (s, N-CH2), 108.2 (d, JCP = 11.5 Hz,
C4), 118.46 (d, JCP = 16.5 Hz, C5), 120.22, 121.56 (d,
JCP = 168.5 Hz, C2), 123.56 (d, JCP = 10.0 Hz, C3)
m/z 286 [M]+. Anal. Calcd for C12H20N3O3P (285): C
50.52, H 7.07, N 14.73. Found: C 50.50, H 7.04, N
14.70.
1H-Pyrrol-3-yl[di(4-morpholyl)]phosphine
Sulfide 9
To compound 8 (0.01 mol) in benzene (30 mL), el-
ementary sulfur (0.01 mol) was added and the re-
action mixture was boiled for 30 min. After evap-
orating the solvent, the residue was recrystallized
from diethyl ether. Yield 68%. mp 127–128◦C. 31P
NMR (DMSO-d6): δ 68.9. H1 (DMSO-d6): δ 3.04 (m,
8H, O CH2); 3.54 (m, 8H, N-CH2); 6.24 (br s, 1H,
H4); 6.85 (br s, 1H, H5); 7.14 (br s, 1H, H2); 11,39
(br s, 1H, N-H). 13C NMR (DMSO-d6): δ 44,98 (s,
O CH2); 66.77 (s, N-CH2); 110,76 (d, JCP = 10.0 Hz,
C4); 112.91; 111.79 (d, JCP = 146.0 Hz, C3); 120.37
(d,JCP = 14.0 Hz, C5); 127.52 (d,JCP = 24.0 Hz C2). m/z
302 [M]+. Anal. Calcd for C12H20N3O2PS (301.35): N
13.94, P 10.28. Found: N 13.74, P 10.03.
1H-Pyrrol-2-yl[di(4-morpholyl)]phosphine
Sulfide 7b
It was obtained similarly to compound 7a. To a
benzene solution of the 2-pyrrolylphosphonous acid
amide (with its 31P NMR signal detected at 85.6
ppm), elementary sulfur (0.01 mol) was added, fol-
lowed by boiling the reaction mixture with a reflux
condenser for 30 min. After evaporating the solvent,
the residue was recrystallized from diethyl ether.
Yield 48%. mp 119–120◦C. 31P NMR (DMSO-d6): δ
1H-Pyrrol-3-yl[di(4-morpholyl)]phosphine
Oxide 10
To a solution of compound 8 (0.01 mol) in benzene
(60 mL), hexachloroethane (0.01 mol) was added
and the reaction mixture was allowed to stand at
room temperature for 5 h. The resulting phospho-
nium salt precipitate was filtered off, washed with
benzene, and dissolved in CH2Cl2 (50 mL). After
shaking the solution with 20% aqueous NaHCO3,
the organic layer was separated, dried over Na2SO4,
and evaporated. The residue was recrystallized from
diethyl ether. Yield 45%. mp 155–157◦C.31P NMR
1
62.7. H NMR (DMSO-d6): δ 2.95 (m, 8H, O CH2),
3.53 (m, 8H, N-CH2), 6.15 (br s, 1H, H4), 6.57 (br s,
1H, H3), 6.99 (br s, 1H, H5), 11.63 (br s, 1H, NH).
m/z 302 [M]+. Anal. Calcd for C12H20N3O2PS (301):
C 47.83, H 6.69, N 13.94. Found: C 47.81, H 6.67, N
13.91.
1H-Pyrrol-3-yl[di(4-morpholyl)]phosphine 8
1
(DMSO-d6): δ 23.7. H NMR (DMSO-d6): δ 2.93 (m,
To an ice-cooled and stirred solution of pyrrole 1
(0.01 mol) and pyridine (0.01 mol) in CH2Cl2 (60
mL), PCl3 (0.01 mol) was added under dry argon.
The reaction mixture was allowed to stand at room
temperature for 5 days (until a 31P NMR signal at
158.7 ppm became a single one), followed by adding
pentane (100 mL), cooling to 0◦C, and decanting the
pentane layer thrice under argon. After dissolving
8H, O CH2), 3.51 (m, 8H, N-CH2), 6.19 (br s, 1H,
H4), 6.91 (br s, 1H, H5), 7.11 (br s, 1H, H2). 13C
NMR (DMSO-d6): δ 44.06 (s, CH2-O), 66.53 (s, CH2-
N), 109.33; 107.91 (d, JCP = 179,0 Hz, C3-P), 110.33
(d, JCP = 11.0 Hz, C4), 119.82 (d, JCP = 14.0 Hz, C5),
125.33 (d, JCP = 20.0 Hz, C2). m/z 286 [M]+. Anal.
Calcd for C12H20N3O3P (285.29): C 50.52, H 7.07, P
10.86. Found: C 50.48, H 7.00, P 10.63.
Heteroatom Chemistry DOI 10.1002/hc

676 Chaikovskaya et al.
[Di(morpholin-4-yl)][3-(4-methoxyphenyl)triaz-
2-enylidene](1H-pyrrol-3-yl)phosphorane 11
2,5-Dimethyl-1H-pyrrol-3-yl[di(4-
morpholyl)]phosphine Oxide 16
To a solution of compound 8 (0.01 mol) in ben-
zene (60 mL), p-methoxyphenyl azide (0.01 mol) was
added and the reaction mixture was stirred at room
temperature for 12 h, followed by evaporation. The
residue was recrystallized from diethyl ether. Yield
72%. 31P NMR (DMSO-d6): δ 36.6. 1H NMR (DMSO-
d6): δ 3.10 (m, 8H, O CH2), 3.55 (m, 8H, N-CH2),
3.74 (s, 3H, O CH3) 6.37 (br s, 1H, H4), 6.86 (d, JHH
= 9.00 Hz, 2H, Ar), 6.95 (br s, 1H, H5), 7.05 (br s,
1H, H2), 7.25 (d, JHH = 9.00 Hz, 2H, Ar) m/z 419
[M]+. Anal. Calcd for C19H27N6O3P (418): C 54.54, H
6.50, N 20.08. Found: C 54.53, H 6.48, N 20.05.
To an ice-cooled solution of 2,5-dimethylpyrrole
16 (0.01 mol) and pyridine (0.01 mol) in CH2Cl2
(50 mL), PCl3 (0.01 mol) was added. The reaction
mixture was allowed to stand for 30 min (until a 31
P
NMR signal at 158.5 ppm was detected), followed by
adding morpholine (0.05 mol). After another 2 h of
standing at room temperature, 30% H2O2 (5 mL) was
added to the reaction mixture; it was stirred for 1 h
and then diluted with H2O (40 mL). The organic layer
was separated, dried over Na2SO4, and evaporated.
The residue was recrystallized from acetone. Yield
85%. mp 174–175◦C. 31P NMR (DMSO-d6): δ 25.5.
1H NMR (DMSO-d6): δ 2.12 (s, CH3), 2.31 (s, CH3),
2.93 (m, 8H, O CH2), 3.51 (m, 8H, N-CH2), 5.63 (s,
1H, Pr), 10.84 (br. s, 1H, NH), 13C NMR (DMSO-d6):
δ 11.92 (s, CH3) 44.57 (s, C-O), 66.49 (d, JCP = 6.5
Hz, C N), 103.71, 102.30 (d, JCP = 177.5 Hz, C3-P),
107.68 (d, JCP = 11.5 Hz, C4), 126.06 (d, JCP = 14.0
Hz, C5), 134.98 (d, JCP = 21.5 Hz, C2). m/z 314 [M]+.
Anal. Calcd for C14H24N3O3P (313): C 53.67, H 7.72,
N 13.41 P 10.86. Found: C 53.65, H 7.70, P 10.63.
[Di(morpholin-4-yl)](4-methoxyphenylimino)-
(1H-pyrrol-3-yl)phosphorane 12
Compound 11 (0.01 mol) was dissolved in toluene
(50 mL) and boiled with a reflux condenser for 5 h.
After evaporating the reaction mixture to dryness,
the residue was recrystallized from diethyl ether.
Yield 93%. mp 152–153◦C. 31P NMR (DMSO-d6): δ
1
13.5. H NMR (DMSO-d6): δ 3.01 (m, 8H, O CH2),
REFERENCES
3.52 (m, 8H, N-CH2), 3.64 (s, 3H, O CH3) 6.37 (br s,
1H, H4), 6.60 (m, 4H, Ar), 6.84 (br s, 1H, H5), 7.15 (br
s, 1H, H2),13C NMR (DMSO-d6): δ 44.71 (s, CH2-O),
54.66 (s, CH3), 66.29 (d, JCP = 6.0 Hz, C N), 106.59;
108.02 (d, JCP = 180.0 Hz, C3-P), 110.83 (d, JCP = 12.0
Hz, C4), 113.77 (s, CAr) 119.38 (d, JCP = 15.0 Hz, C2),
122.99 (d, JCP = 15.0 Hz, CAr) 125.54 (d, JCP = 19.0
Hz, C5), 143.55 (s, CAr), 150.90 (s, CAr), m/z 391 [M]+.
Anal. Calcd for C19H27N4O3P (390): C 58.45, H 6.97,
N 14.35. Found: C 58.44, H 6.96, N 14.33.
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Methyl[di(morpholin-4-yl)](1H-pyrrol-3-
yl)phosphonium 13
To a solution of compound 8 (0.01 mol) in benzene
(50 mL), CH3I (0.02 mol) was added at room tem-
perature and the reaction mixture was stirred for
12 h, followed by decantation of the benzene solu-
tion and recrystallization of the residue from diethyl
ether. Yield 95%. mp 135–136◦C.31P NMR (DMSO-
d6): δ 50.4. 1H NMR (DMSO-d6): δ 2.38 (d, JCP = 15.09
Hz, CH3), 2.98 (m, 8H, O CH2), 3.63 (m, 8H, N-CH2),
6.56 (br. s, 1H, H4), 7.17 (br. s, 1H, H5), 7.68 (br. s,
1H, H2), m/z 286 [M]+. Anal. Calcd for C13H24N3O2P
(285): C 54.72, H 8.48, N 14.73. Found: C 54.70, H
8.45, N 14.72.
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Heteroatom Chemistry DOI 10.1002/hc