One-step transformation of ammonium dialkyl phosphoroselenoates into dialkyl phosphoramidates

Article abstract of DOI:10.1002/hc.10110

Ammonium dialkyl phosphoroselenoates are directly converted into the dialkyl phosphoramidates by iodosobenzene and iodoxybenzene. The inversion of configuration at the phosphorus atom, using model diastereoisomeric ammonium cis- and trans-2-oxo-2-seleno-4-methyl-1,3,2-dioxaphosphinan system, was observed. The mechanistic scheme of this transformation is discussed.

Full text of DOI:10.1002/hc.10110

Heteroatom Chemistry
Volume 14, Number 2, 2003
One-Step Transformation of Ammonium
Dialkyl Phosphoroselenoates into Dialkyl
Phosphoramidates
Graz˙yna Mielniczak and Andrzej Lꢀ opusin´ski
Department of Heteroatom Chemistry, Centre of Molecular and Macromolecular Studies,
90-363 Lo´dz´, Sienkiewicza 112, Poland
ꢀ
Received 21 May 2002; revised 29 July 2002
phosphorothioic acid esters in their reactions
with DMSO [19,20] as well as potassium dialkyl
phosphorothioate in the reaction with peroxymono-
sulfate (OxoneꢀR ) [21], were reported. Recently,
we described [22] the quantitative formation of
bis(dialkoxyphosphinyl) disulfide as a major prod-
uct of the oxidation reaction of ammonium dialkyl
phosphorothioate by iodoxybenzene.
Herein we report that the ammonium dialkyl
phosphoroselenoates 1a–c undergo facile reactions
with iodoso (2) or iodoxybenzene (3) to produce di-
alkyl phosphoramidates 4a–c. The formation of am-
monium dialkyl hydrogen phosphates 5a–c and dis-
elenide 6 in same cases of these reactions was also
observed (Scheme 1).
ABSTRACT: Ammonium dialkyl phosphorose-
lenoates are directly converted into the dialkyl
phosphoramidates by iodosobenzene and iodoxy-
benzene. The inversion of configuration at the
phosphorus atom, using model diastereoisomeric
ammonium cis- and trans-2-oxo-2-seleno-4-methyl-
1,3,2-dioxaphosphinan system, was observed. The
mechanistic scheme of this transformation is dis-
ꢀ
C
cussed. 2003 Wiley Periodicals, Inc. Heteroatom Chem
14:121–127, 2003; Published online in Wiley InterScience
(www.interscience.wiley.com). DOI 10.1002/hc.10110
INTRODUCTION
The reactions were performed in an acetonitrile
solution at room temperature in the absence or pres-
ence of montmorillonite K10 used in 0.5 weight ratio
in relation to 2 or 3, respectively. Efficient oxidation
reaction with the use of iodosobenzene activated by
montmorillonite K10 as well as the natural clays,
namely KSF and bentonite, was recently reported
[23]. 31P NMR spectroscopy was used to monitor the
progress of the reactions. The reactions were rapid
and precipitation of elemental selenium from the so-
lution in the short time after mixing of the reagents
was observed. Results of the experiments are given
in Table 1.
Reactions
of
organic
monothio-,
dithio-,
monoseleno-, and selenothioacids of phosphorus,
as well as their metal or ammonium salts with
0.5 equiv of halogens or sulfuryl chloride, are
commonly used as methods of choice for the syn-
thesis of organophosphorus disulfides [1–9] and
diselenides [10–13]. Similarly, high yield formation
of bis(thiophosphoryl)disulfides in the oxidation of
phosphorodithioic acids and their salts with nitric
acid, nitrogen oxides [14–17], hydrogen peroxides
[6,7], and dimethyl sulfoxide (DMSO) [18] was
also observed. On the other hand, the oxidative
desulfurization of phosphino-, phosphono-, and
The reaction of 1a with 2 performed in the ab-
sence as well as in the presence of montmorillonite
K10 gave only poor yields of amide 4a (runs 1 and 2).
During the oxidation of 1a with 2 in the presence of
montmorillonite K10, the formation of diselenide 6
Correspondence to: Andrzej Lꢀ opusin´ski; e-mail: lopuch@bilbo.
cbmm.lodz.pl.
c
ꢀ
2003 Wiley Periodicals, Inc.
121

122 Mielniczak and ꢀLopusin´ski
SCHEME 1
as a major product was observed. Under similar reac-
tion conditions, the oxidation of 1a with iodoxyben-
zene (3) produced amidate 4a in a satisfactory yield
(runs 3 and 4). The obtained results suggest that the
use of montmorillonite K10 in the reaction of salts
1a,b with either 2 or 3 had a negative influence on
the yield of the formed amidate 4a (runs 2 and 3).
On the other hand, the reaction between 3 and
ammonium t-butylphenyl/phosphinoselenoate (1c)
occurred in boiling acetonitrile solution, in the pres-
ence of montmorillonite K10. Under these con-
ditions, the formation of a major product am-
monium salt 5c and only a small amount of
t-butylphenylphosphinic amide (4c) was observed.
To examine the stereochemical course of
the transformation of ammonium phosphorose-
lenoates → phosphoramidates, the ammonium salts
trans- and cis-2-hydroxy-2-seleno-4-methyl-1,3,2-
dioxaphosphinans (8) were selected. They were
synthesized by the reaction of the elemental
selenium with cis- and trans-2-hydrogen-2-oxo-
4-methyl-1,3,2-dioxaphosphinans (7) respectively.
The synthesis was performed in a liquid am-
monia solution, according to our method de-
scribed earlier [24]. Then, trans- and cis-8 were
transformed by reaction with methyl iodide into
trans- and cis-2-methylseleno-2-oxo-4-methyl-1,3,2-
dioxaphosphinans (9), respectively. The cis and trans
configuration of esters 9 was established earlier [25].
The reaction sequence (Scheme 2) shows that the ad-
dition of elemental selenium to the cyclic cis- and
SCHEME 2
trans-phosphites 7 in the liquid ammonia solution
is a completely stereospecific process. The possible
epimerization of the labile trans-7 into thermody-
namically stable cis-7 was not observed under these
reaction conditions (Scheme 2). The obtained results
correspond well with known stereochemistry of the
TABLE 1 Reactions of Salts 1a–c with 2 or 3 in Acetonitrile Solution at 20◦C
Products Yield (%)
Substrate
Run
Oxidant
Activator
1
2
3
4
5
6
R Rꢁ OEt; Rꢁꢁ H 1a
2
2
3
3
3
3
−
+
+
−
−
+
Rꢁꢁ H 4a (36)a
4a (28)a
5a (12)a
–
1a
5a (9)a
6 (63)a
1a
1a
4a (74)a
–
–
–
–
–
–
4a (85)a (71)b
4b (42)a (26)b
4c (12)a
R Rꢁ OEt; Rꢁꢁ Et 1b
R But , Rꢁ Ph, Rꢁꢁ H 1c
5b (26)a
5c (72)a (66)b
aYields calculated from 31P NMR spectra.
bYields after isolation.

One-Step Transformation of Ammonium Dialkyl Phosphoroselenoates into Dialkyl Phosphoramidates 123
addition of elemental sulfur and selenium to the cis-
and trans-7 performed in the presence of amines at
room temperature [25].
The individual isomers, trans-8 and cis-8 were
treated with iodoxybenzene 3 in acetonitrile solution
at room temperature, and reaction course was mon-
itored by 31P NMR spectroscopy. Within few minutes
of the addition of 3 to the stirred suspension of trans-
8 in acetonitrile, yellow color of the reaction mixture
appeared, and after about 1 h the slow precipitation
of fine red-brown solid material was observed. After
12 h, the formation of 52% of trans-2-amino-2-oxo-
4-methyl-1,3,2-dioxaphosphinan (10, δ 31P 9.4) and
48% of ammonium 2-hydroxy-2-oxo-4-methyl-1,3,2-
dioxaphosphinan (11, δ 31P −4.68) was identified in
the reaction mixture.
Under similar reaction conditions, cis-8 reacts
more readily than isomer trans-8 with 3 and the
formation of amidate 10, 55.6% yield, (cis-10 δ 6.4
(86%) and trans-10, δ 9.4 (14%)), together with am-
monium salt 11 (44%) was registered by 31P NMR.
The obtained results show that the oxidation of trans-
and cis-8 by 3 leads to the formation of the amidates
trans- and cis-10, respectively (Scheme 3).
The configurational assignment for cis- and
trans-amidates 10 has been already established [26].
The data shown in Scheme 3 evidenced the inversion
of configuration at phosphorus atom, as the stereo-
chemical result of 8 → 10 transformation. Both start-
ing isomers cis- and trans-8 have the same absolute
configuration as the product of their transformations
10, which results from the priority order of the sub-
stituents on the phosphorus. However, the spatial
arrangements of the substituents around the phos-
phorus in the products 10, in comparison to their
precursors 8, are changed. The obtained results of-
fer a direct reaction the transformation of the ammo-
nium dialkyl phosphoroselenoates into dialkyl phos-
phoramidates. In this process the amido groups in
products 4a–c and 10 origins formally from the am-
monium cation of the salts moieties 1a–c and 8.
The observed formation of the ammonium phos-
phates 5a–c and 11 in these reactions can be due to
the direct oxidative deselenization of 1 and 8 by 2
and/or 3, similar to the well-known oxidative desul-
phurization of organic thioacids of phosphorus as
well as their salts [19–21]. Alternatively, the observed
formation of ammonium phosphates 5a–c and 11 re-
sult most probably from the participation of water
in this reactions. We have observed that the reaction
of iodoxybenzene 3 with cis-8 performed in a solu-
tion of acetonitrile/water (3:1) result in the formation
of the ammonium 2-hydroxy-2-oxo-4-methyl-1,3,2-
dioxaphosphinan (11) as the sole reaction product
(Scheme 4).
SCHEME 3
Most probably, in the first step of the reaction of
salts 1 with 3, the oxygen atom transfer from 3 to the
selenium atom in 1 takes place and the intermediate
product 12 is formed (Scheme 5).
The proton transfer from the ammonium cation
to oxygen gave selenenic acid 13. Subsequent for-
mation of seleninic acid 14 is also possible. The
nucleophilic attack of ammonia on the phospho-
rus atom in both 13 and 14 leads to the forma-
tion of the corresponding amidates with inversion
SCHEME 4

124 Mielniczak and ꢀLopusin´ski
diethyl phosphite in the presence of ethylamine in
1
toluene solution at room temperature, 31P{ H} NMR
(CDCl3): δ 51.1 J31P-77Se 775 Hz, MS–FAB m/z, 217
[M − NH4].
t-Butylphenyl Phosphinoselenoate (1c)
Reaction flask containing mixture of 0.45
g
(0.24 mmol) t-butylphenylphosphine oxide [28] and
0.2 g (0.24 mmol) selenium in a solution of 25 ml
of liquid ammonia was cooled and stirred at −35◦C
for 8 h. The cooling bath was removed and gaseous
ammonia was distilled off. The crude solid was dis-
solved in dry CH2Cl2 (30 ml) and the solution was
filtered through Cellite. The solvent was evaporated
in vacuo and the remaining crude salt was crystal-
lized twice from dry acetonitrile. Salt 1c 1.37 g (86%)
was obtained as a pale yellow prism, mp 74–75◦C,
1
31P{ H} NMR (D2O): δ 79.8, J31P-77Se 601 Hz, MS–FAB
m/z 261 [M − NH4] (calculated for 80Se). Anal. calcd.
for C10H18NOPSe: C, 43.13; H, 6.52; N, 5.03; P, 11.13;
Found: C, 43.40; H, 6.26; N, 5.25; P, 11.39.
SCHEME 5
of configuration at phosphorus atom. Formation of
both selenic 15 and seleninic 16 acids as unstable
reaction products as well as their being the final the
sources of the water molecules cannot be excluded.
The easy proton abstraction by strongly basic oxy-
gen atom bounded to the selenium is known from
the literature [27].
Further studies on the synthetic and mechanistic
aspects of the oxidation reaction of ammonium salts
of organophosphorus monoselenic acids by iodoxy-
benzene are in progress.
Ammonium trans-2-Hydroxy-2-seleno-4-methyl-
1,3,2-dioxaphosphinan (8)
In a stirred suspension of finely powdered selenium
(0.27 g; 0.34 mmol) in 30 ml of dry liquid ammo-
nia, 0.47 g (0.34 mmol) of cis-2-hydrogen-2-oxo-4-
methyl-1,3,2-dioxaphosphinan (7) [29] in 2 ml of
dry ethyl ether was added at −35◦C. The reaction
mixture was stirred on the bath at temperatures be-
tween −33 and −35◦C for 8 h. Then the cooling bath
was removed and stirring was continued until all
amount of ammonia was distilled off. The remain-
ing crude solid product was recrystallized from i-
propanol/ethyl ether, yield trans-8 0.69 g (88.5%),
EXPERIMENTAL
1
The solvents were dried by standard methods be-
fore use. 1H NMR spectra were determined at 200.13
MHz with a Bruker AC 200 spectrometer, using
TMS as an internal standard. 31P NMR spectra were
taken on a Bruker AC 200 spectrometer at 81 MHz.
Positive chemicals shifts are downfield from 85%
H3PO4 used as an external reference. LSIMS spec-
tra were recorded on a Finnigan MAT 95 spectrom-
eter, in glycerol or 4-nitrobenzyl alcohol, using ce-
sium as the primary ion beam. CIMS spectra were
recorded on the same apparatus, using isobutane as
a reagent gas. Ammonium t-butylphenyl phosphi-
noselenoate 1c was synthesized by the reaction of
t-butylphenylphosphine oxide with elemental sele-
nium in the liquid ammonia solution. Synthesis of
1a was described recently [24]. Ethylammonium di-
ethyl phosphoroselenoate 1b was synthesized as pale
yellow oil by the addition of elemental selenium to
mp 177–178◦C, 31P{ H} NMR (D2O): δ 45.67, J31P-77Se
735 Hz; MS–FAB m/z 215 [M − NH4] (calculated for
80Se); 1H: δ 1.24 (dd, 3H, JH-CH 6.31 Hz, JP-H 1.82 Hz);
δ 1.72–1.86 (m, 2H); δ 4.03–4.313 (m, 1H); δ 4.29–4.35
(m, 1H); δ 4.52–4.60 (m, 1H); IR (KBr): 545.75 (m),
599.32 (m), 756.99 (s), 791.36 (m), 845.25 (w), 885.17
(w), 921.81 (m), 962.74 (w), 980.57 (w), 1028.71 (m),
1070.30 (s), 1079.94 (s), 1120.44 (s), 1156.45 (s),
1224.01 (w), 1250.51 (w), 1375.00 (m), 1385.17 (m),
1462.76 (m), 1655.37 (vw), 2971.79 (m), 3179.60 (m),
3412.27 (w) cm−1. Anal. calcd. for C4H12NO3PSe: C,
20.70; H, 5.21; N, 6.03; P, 13.34. Found: C, 20.86; H,
5.21; N, 6.08; P, 14.24.
Reaction of trans-8 with Methyl Iodide
To a stirred suspension of trans-8 (δ 31P 45.7;
0.23 g; 1 mmol) in 15 ml of dry acetonitrile, 0.35 g

One-Step Transformation of Ammonium Dialkyl Phosphoroselenoates into Dialkyl Phosphoramidates 125
(2.5 mmol) of methyl iodide was added. After 18 h
δ 12.9 (51%). During the prolongation of the reaction
time the broad line at 12.9 disappeared slowly and
a mixture of organophosphorus compounds with δ
−0.1, 3.6, 10.2, 11.5, 12.6 near amidate 4a (42%) and
salt 5a (14%) was formed.
the solvent was evaporated in vacuo and the remain-
ing oily product was dissolved in 20 ml of chloroform
and filtered. Evaporation of filtrate and evacuation
of the remaining material at 20◦C under pressure
1 mm Hg for 4 h afforded trans-2-methylseleno-
2-oxo-4-methyl-1,3,2-dioxaphosphinan (9) 0.21 g
Oxidation of 1a by 2 in the Presence
of Montmorillonite K10
1
(94%), mp 55–56◦C, 31P{ H} NMR (CDCl3): δ 13.18,
J31P-77Se 469 Hz; (Ref. [25] mp 58–59◦C, δ 31P 11.7,
J31P-77Se 444.7 Hz); CIMS m/z 231 [M + 1] (calculated
for 80Se).
In a stirred suspension of 0.3 g (1.38 mmol) of 2
and 0.15 g of montmorillonite K10 in 10 ml ace-
tonitrile, 0.32 g (1.38 mmol) of 1a dissolved in 5 ml
of acetonitrile was added at room temperature. Af-
ter 2 h the following organophosphorus products
were observed: amidate 4a with δ 9.92 (28%), salt
5a with δ −0.49 (9%), tetraethyl pyrophosphate δ
13.0 (5%), and a compound characterized by broad
line at δ 19.63 (63%), J31P-77Se 548 Hz. The broad
line at δ 19.6 is most probably a characteristic
of bis(diethylphosphinyl)diselenide (6a) (Ref. [30]
δ 31P 13.0, J31P-77Se 580 Hz; Ref. [31] δ 31P 11.1, J31P-77Se
498 Hz).
Ammonium cis-2-Hydroxy-2-seleno-4-methyl-
1,3,2-dioxaphosphinan (8)
In the reaction of 1.46 g (10.7 mmol) of trans-2-
hydrogen-2-oxo-4-methyl-1,3,2-dioxaphosphinan(7)
[29], contaminated by 8% cis-(7) isomer, with 0.83 g
(10.7 mmol) of selenium, in 35 ml liquid ammonia
solution, performed as described above, a mixture
of two products δ 31P 47.62 (93%) and δ 31P 43.32
(7%) was obtained. From this, 1.92 g (77% yield),
1
mp 140–141◦C (i-PrOH/Et2O) of pure cis-8 (31P{ H}
NMR (D2O): δ 47.58, J31P-77Se 780.6 Hz, MS–FAB, m/z
215 [M − NH4]) was isolated by crystallization. 1H: δ
Reaction of 1a with Iodoxybenzene 3
1.19 (dd, 3H, JH-CH 6.39Hz, JP-H 1.13 Hz); δ 1.69–1.76
To a stirred solution of 1.17 g (5 mmol) of 1a in a dry
acetonitrile (10 ml) at 20◦C under nitrogen, 1.18 g
(5 mmol) of 3 was added. Stirring was continued
for 1 h and to the red-brown solution were added
2 g of Cellite and neutral Al2O3 (1:1). The reaction
mixture was stirred for the next 25 min and solid
materials were filtered off and washed with CH3CN
(3 × 5 ml). The solvent was distilled off in vacuo at
room temperature and yellow colored viscous liquid
was obtained. In this, the presence of diethyl phos-
phoramidate 4a (δ 9.9; 85%) together with two other
unidentified products (δ 12.2; 10% and δ 6.1; 5%) was
found by 31P NMR. From this mixture, 0.56 g (71%)
of 4a with mp 53–55◦C (Ref. [32] mp 55.5◦C, Ref.
[33] δ 31P 10.9) was separated by flash column chro-
matography, eluent: petroleum ether (bp 40–60◦C):
diethyl ether (4:1), MS–FAB m/z 152 [M − 1], m/z 154
[M + 1].
3
(m, 1H); δ 1.83 (m, 1H); δ 4.02 (m, 1H); δ 4.25 (m,
1H); δ 4.5 (m, 1H); IR (KBr): 552.78 (w), 593.97 (vw),
765.60 (m), 844.21 (w), 880.80 (m), 923.74 (s), 962.14
(s), 978.53 (m), 1025.83 (m), 1066.44 (vs), 1133.34
(m), 1156.65 (m), 1251.58 (vw), 1386.57 (m), 2972.63
(m), 3153.65 (m), 3414.42 (w) cm−1. Anal. calcd. for
C4H12NO3PSe: C, 20.70; H, 5.21; N, 6.03; P, 13.34.
Found: C, 20.64; H, 5.21; N, 6.06; P, 14.24.
Reaction of cis-8 with Methyl Iodide
In the reaction of 0.102 g (0.43 mmol) of 8 (93% cis,
7% trans) with 0.2 g (1.4 mmol) of methyl iodide, in
15 ml of acetonitrile, 0.09 g (96%) of cis-(9) was ob-
1
tained as an oily liquid, n20 = 1.5173, 31P{ H} NMR
D
(CDCl3): δ 17.35, J31P-77Se 501 Hz, CIMS m/z 231 [M
+ 1] (calculated for 80Se) (Ref. [25] δ 31P 14.0, J31P-77Se
476.3 Hz).
Reaction of 1b with Iodoxybenzene 3
Reaction of 1a with Iodosobenzene 2
To a stirred solution of 2.8 g (10.8 mmol) of 1b
in 20 ml of acetonitrile, 2.3 g (10.8 mmol) of 3
at 20◦C was added and stirring was continued for
1 h. 31P NMR analysis of the reaction mixture per-
formed after this showed the presence of diethyl
N-ethylphosphoramidate (4b; δ 9.47; 42%), ethy-
lammonium diethylhydrogen phosphate (5b; δ 0.15;
26%), and two unidentified products (δ 11.66; 9%
and δ 4.29; 22%). The solvent was distilled off and
In a stirred solution of 0.23 g (1 mmol) of 1a in 5 ml of
acetonitrile, 0.22 g (1 mmol) of 2 was added at 20◦C
and stirred continuously for 1 h. 31P NMR analysis
of the reaction mixture showed the presence of am-
monium diethyl hydrogen phosphate (5a; δ −0.42;
12%) and diethyl phosphoroamidate (4a; δ 9.8; 36%).
In 31P NMR spectrum of the reaction mixture, a
broad signal of unidentified product was observed at

126 Mielniczak and ꢀLopusin´ski
red-brown viscous liquid was obtained. The MS–FAB
and CIMS analysis of this crude material showed the
presence of lines: m/z 153, characteristic for anion
(EtO)2PO−2 and m/z 182 [M + 1], characteristic for 4b.
To this 20 ml of CHCl3 and 2 g of Cellite was added.
The solution was stirred for 20 min and the solid ma-
terial was filtered off and washed with chloroform
(2 × 10 ml). The solution was distilled off and from
the residual oil amidate 4b (0.43 g; 26%) was sep-
the next 12 h. The solvent was distilled off, and the
remaining black-gray colored syrupy material was
dissolved in 15 ml of ethanol and filtered through
1
Cellite. After removal of the solvent, 31P{ H} NMR
(EtOD) spectrum of the crude product showed the
presence of two lines at δ 9.40 (52%), which was iden-
tified as a characteristic for amidate trans-10 (Ref.
[26] δ 31P 9.1 (EtOD)), and δ −4.68 (48%) characteris-
tic for ammonium-2-hydroxy-2-oxo-4-methyl-1,3,2-
dioxaphosphinan salt 11. MS–FAB m/z 152 [10 + 1],
m/z 151 [anion 11].
1
arated by distillation. 31P{ H} NMR (CDCl3): δ 9.87,
bp 63–66◦C/0.2–0.3 mm Hg, (bath temp. 100–105◦C),
n20 = 1.4286 (Ref. [34] δ31P 9.9, n20 = 1.4300).
D
D
Reaction of cis-8 with 3
Reaction of Salt 1c with 3 in the Presence
To a stirred solution of 0.23 g (1 mmol) of cis-8 in
5 ml of acetonitrile, 0.23 g (1 mmol) of 3 was added
at room temperature. After 40 min the formation
of red-brown precipitate was observed. Stirring was
continued for the next 12 h. The solvent was evapo-
rated and the brown syrupy oily liquid was obtained.
In this product, 56% of amidate 10, (86% of cis-10 δ
6.40 and 14% of trans-10 δ 9.47) (Ref. [26] δ 31P for
cis-10 6.0) together with 44% of the salt 11 were iden-
of Montmorillonite K10
A mixture of 0.27 g (1 mmol) of 1c and 0.23 g (1
mmol) of 3 was stirred and heated under reflux in
15 ml of dry acetonitrile for 1.5 h. 31P NMR spec-
trum of the reaction solution showed the presence
of only one line at δ 78.0 characteristic for the sub-
strate 1c. To this reaction solution 0.1 g of dry mont-
morillonite K10 was added, and the reaction mixture
was heated under reflux for 1.5 h. After this the for-
mation of salt 5c (δ 44.30; 72%) together with 12%
yield of amidate 4c (δ 39.33; Ref. [35] δ 31P 41.4)
and another unidentified organophosphorus com-
pounds (δ 50.48; 9% and δ 49.9; 7%) was observed
by 31P NMR. The solvent was distilled off and into
the remaining red-brown, syrupy liquid of 20 ml dry
ethanol, 2.0 g charcoal, and 2.0 g Cellite were added.
The mixture was stirred for 30 min at 20◦C and fil-
tered through Cellite. The solvent was distilled off
and the remaining oily, slowly solidifing liquid was
keep standing for 1 h under pressure 1 mm Hg at tem-
perature 25◦C. Recrystallization of crude material
from i-propanol/ethyl ether gave 0.13 g (66%), mp
153–154◦C, MS–FAB m/z 197 [ButPhP(O)O−] of am-
monium t-butylphenyl phosphinoate (5c). The iso-
lated salt 5c was identical with the one obtained in
an independent way in the reaction of t-butylphenyl
phosphinic acid [28] with gaseous ammonia in chlo-
1
tified by analysis of 31P{ H} NMR spectra; MS–FAB
m/z 152 [10 + 1], m/z 151 [anion 11].
Reaction of cis-8 with 3 in the Solution
of Acetonitrile–Water (3:1)
A stirred solution of 0.23 g (1 mmol) of salt cis-8 in
10 ml acetonitrile–water (3:1) was treated at room
temperature with 0.23 g (1 mmol) of 3. Immediate
precipitation of red-brown solid material from the
reaction solution was observed. Stirring was contin-
ued for the next 4 h. 31P NMR analysis of the reaction
mixture showed only one product with δ −4.14. No
change in this δ 31P value, after treating the sample
of the reaction solution with gaseous ammonia, was
observed. The reaction solution was filtered through
Cellite and the solvents were distilled off. The re-
maining material was kept standing at a temperature
range of 15–20◦C under pressure of 0.1–0.5 mm Hg
for 6 h and 0.12 g (75%) of a syrupy oil that slowly
1
roform solution, 31P{ H} NMR (D2O): δ 43.05, mp
153–154◦ C, Anal. calcd. for C10H18NO2P: C, 55.81;
H, 8.42; N, 6.50; P, 14.39; Found: C, 55.63; H, 8.16;
N, 8.38; P, 14.26.
1
solidified at 5◦C (31P{ H} NMR δ: −4.04, MS–FAB m/z
151 [M − NH4]) was obtained. The same product,
synthesized on the independent route in the reac-
tion of gaseous ammonia with 2-hydroxy-2-oxo-4-
methyl-1,3,2-dioxaphosphinan [36] in ethanol solu-
Reaction of trans-8 with 3
tion, was syrupy oily liquid, 31P{ H} NMR δ: −3.67.
1
In a stirred solution of 0.34 g (1.46 mmol) of trans-8
in 5 ml dry acetonitrile, 0.34 g (1.46 mmol) of dry
iodoxybenzene (3) was added at 20◦C. Stirring was
continued at this temperature, and after 90 min the
formation of red-brown precipitate in the reaction
mixture was observed. Stirring was continued for
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