Synthesis of phosphorus derivatives from 1,3-dioxolan-2-one

Article abstract of DOI:10.1080/714040962

A new route for the synthesis of some mixed organic phosphorus compounds from 1,3-dioxolan-2-one is reported. By heating a mixture of phosphorus-chlorine derivatives and 1,3-dioxolan-2-one in the presence of a catalyst, mixed phosphorus derivatives having 2-chloroethyl ester groups could be obtained. A wide range of phosphorus derivatives can be obtained using this method.

Full text of DOI:10.1080/714040962

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Phosphorus, Sulfur, and Silicon and the Related
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Synthesis of Phosphorus Derivatives from 1,3-
Dioxolan-2-one
Gheorghe Ilia a , Alina Bora a , Smaranda Iliescu a , Adriana Popa a & Gheorghe Dehelean a
a Institute of Chemistry, Timisoara, Romania
Published online: 18 Jun 2010.
To cite this article: Gheorghe Ilia , Alina Bora , Smaranda Iliescu , Adriana Popa & Gheorghe Dehelean (2003) Synthesis of
Phosphorus Derivatives from 1,3-Dioxolan-2-one, Phosphorus, Sulfur, and Silicon and the Related Elements, 178:11, 2491-2496,
DOI: 10.1080/714040962
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Phosphorus, Sulfur, and Silicon, 178:2491–2496, 2003
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Copyright Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500390235686
SYNTHESIS OF PHOSPHORUS DERIVATIVES
FROM 1,3-DIOXOLAN-2-ONE
Gheorghe Ilia, Alina Bora, Smaranda Iliescu, Adriana Popa,
and Gheorghe Dehelean
Institute of Chemistry, Timisoara, Romania
(Received May 15, 2003; in final form June 10, 2003)
A new route for the synthesis of some mixed organic phosphorus com-
pounds from 1,3-dioxolan-2-one is reported. By heating a mixture of
phosphorus-chlorine derivatives and 1,3-dioxolan-2-one in the presence
of a catalyst, mixed phosphorus derivatives having 2-chloroethyl ester
groups could be obtained. A wide range of phosphorus derivatives can
be obtained using this method.
Keywords: 1,3-Dioxolan-2-one; 2-chloroethyl ester; mixed phosphate;
phosphinate; phosphine oxide; phosphinite; phosphite; ring opening
Phosphorus derivatives containing 2-chloroethyl groups, bonded di-
rectly to the phosphorus atom or though an oxygen atom, are important
organic phosphorus compounds. They are used as flame-retardants,
plant growth regulators, or lubricants.1−6
The literature7−11 mentions other methods for the synthesis of mixed
phosphorus derivatives having 2-chloroethyl ester groups: from 2-
chloroethanol (Scheme 1) or ethylene oxide (Scheme 2). These methods
have some inconveniences such as uncontrolled reactions and difficul-
ties in product separation.
SCHEME 1
No data concerning the reaction between phosphorus-chlorine
derivatives and 1,3-dioxolan-2-one were found. The investigation was
Address correspondence to Gheorghe Ilia, Institute of Chemistry, 24 M. Viteazul Bv.,
1900 Timisoara, Romania. E-mail: ilia@acad-tim.utt.ro
2491

2492
G. Ilia et al.
SCHEME 2
started in order to find out if 1,3-dioxolan-2-one could react with those
kinds of phosphorus derivatives. Here, we report the results obtained
from the study of the reaction of phosphorus derivatives and 1,3-
dioxolan-2-one (ethylene carbonate) (Scheme 3).
SCHEME 3
RESULTS AND DISCUSSION
The reaction of diphenylchlorophosphate 1a, 1,3-dioxolan-2-one and a
catalyst (LiF or LiCl) was investigated. Heating the mixture at 120–
130◦C, only little carbon dioxide was released. Increasing the tempera-
ture increases the amount of carbon dioxide released. Reaction products
were separated by Gas-Chromatography (column: OV-17/Gas Chrome
Q; column temperature: 240◦C; injector temperature: 280◦C; detector
temperature: 270◦C; carrier gas: hydrogen) using as standards, com-
mercial products, or synthesized compounds from 2-chloroethanol and
diphenylchlorophosphate or phenyldichlorophosphate in the presence
of triethylamine. During the investigation it was observed that three
peaks appear in the chromatogram (Figure 1). The retention times for
the studied compounds are in concordance with their molecular struc-
ture. These compounds also were separated using columns containing
different stationary phases (Table I).
Thus, in all cases, the retention indices increase with increasing of
molar mass and the polarity of the stationary phase. The calculated
values are the same or a little bit higher than experimental ones.
They were identified as 2-chloroethyl-diphenylphosphate 3a (31P
NMR: 11.4 ppm), bis(2-chloroethyl) phenylphosphate 6 (31P NMR:
3.7 ppm) and triphenylphosphate 4. Concerning these data, it was
concluded that one of the reagent, diphenylchlorophosphate, gives a

Mixed Phosphorus Derivatives
2493
FIGURE 1 GC chromatogram for studied compounds: bis (2-chloroethyl)
phenylphosphate-peak 1, 2-chloroethyldiphenylphosphate-peak 2, triphenyl-
phosphate-peak 3.
SCHEME 4
partially disproportion reaction (Scheme 4) and the compound 5 reacts
with 1,3-dioxolan-2-one giving the product 6 (Scheme 5).
In both cases, the reactions take place by ring opening of the 1,3-
dioxolan-2-one and the migration of chlorine from the phosphorus atom
to the carbon atom. Then we tried to find another catalyst that could de-
crease the reaction temperature, increase the yield of 3a, and decrease
SCHEME 5

2494
G. Ilia et al.
TABLE I Experimental and Calculated Retention
Indices (I) for Compounds 1–4 from Figure 1
IOV−1
IOV−17
IOV−225
Compound Iexp. Icalc.
Iexp.
Icalc. Iexp. Icalc.
1
2
3
4
1735
1929
2140
2358
—
1942
2150
—
2104
2332
2566
2816
—
2340
2565
—
2778
2943
3132
3340
—
2952
3152
—
the side reactions. The best results were obtained when guanidine sul-
fate (GS) or guanidine carbonate (GC) were used (Table II).
Other 2-chloro derivatives were obtained by using guanidine carbon-
ate as catalyst. Table III presents reaction conditions and the obtained
results.
For compound (3c) the yield was lower because 2-chloroethyl-
diphenylposphinite at the reaction temperature undergoes a Mikaelis-
Arbuzov reaction which leads to phosphine oxide (7) (Scheme 6). 31P
NMR (standard 85% H3PO4) has shown two peaks at −36.3 ppm
and −112.5 ppm, corresponding to compounds (7) and (3c) respec-
tively. Compound 7 was obtained in 25% yield by recrystalization from
benzene-hexane (m.p. 125–127◦C).12
SCHEME 6
All compounds were obtained by a simple method which could be
controlled through the reaction temperature, catalyst, and the amount
of carbon dioxide released.
EXPERIMENTAL
From Ethylene Carbonate
A mixture of phosphorus-chlorine derivative 1a–f (0.02 mmol), 1,3-
dioxolan-2-one (0.03 mmol) and the catalyst (0.02 g) was heated at a se-
lected temperature and kept until all carbon dioxide was released. The
mixture was dissolved in chloroform or benzene, washed with H2SO4

Mixed Phosphorus Derivatives
2495
TABLE II Synthesis of Mixed Phosphates
Reaction conditions
Temp.,◦C
Time, h Catalyst Yield (3a) % Yield (4) % Yield (6) %
120
160
170
120
160
170
150
120
2
2
3
2
2
3
3
3
LiCl
LiCl
LiCl
LiF
LiF
LiF
GS
3
22
28
5
30
35
50
59
5
12
18
7
16
20
7
1
8
10
2
7
10
5
GC
3
3
Yield-based on 1a used.
0.5 N (twice with NaHCO3 5%, then twice with water) the layers sep-
arated, and the organic layer dried with anhydrous Na2SO4 (except
3c which was separated without washing); the solvent was removed
by distillation and the products separated using a semi-preparative
HPLC-MD1510 Jasco. 31P NMR spectra were performed with a Bruker
Avance DRX 400.
Classical Method for 3a and 6 (Used as Standards)
3a was synthesized from diphenylchlorophosphate (0.1 mmol), 2-
chloroethanol (0.12 mmol), and triethylamine (0.1 mmol) at 25◦C for
5 h, chlorohydrate filtered, and then the mixture purified by distilla-
tion under reduced pressure (b.p.2 170–176◦C; d201.2912, lit.8 b.p.0.5−1
168–173). 6 was synthesized from phenyldichlorophosphate (0.1 mmol),
2-chloroethanol (0.22 mmol), and triethylamine (0.2 mmol) at 25◦C, for
7 h, chlorohydrate filtered, then the mixture purified by distillation
under reduced pressure (b.p.1 164–167◦C; d201.398, lit.8 b.p.0.2–0.5 160–
163).
TABLE III Synthesis of 2-Chloroderivatives of Phosphorus Compounds
Reaction temp.,
◦C
Yield,
%
b.p.,
31P NMR,
ppm
Comp.
R
X
◦C/mm Hg
3b
3c
3d
3e
3f
C6H5
C6H5
C2H5O
C2H5
O
95–110
115–125
75–90
90–100
90–100
65.3
40.7
50.4
39.8
36.5
173–177/1
110–114/3 13
76–78/3
−30.8
−110.5
−137.0
−71.5
None
None
S
112–115/5
(CH3)2N None
76–79/8 14
−138.2

2496
G. Ilia et al.
CONCLUSIONS
The method used is not mentioned in the literature and it allowed
us to synthesize mixed 2-chloroethyl derivatives. The performed stud-
ies showed that the catalyst and the temperature are essentials for
this reaction. The best catalyst was guanidine carbonate. The best re-
sults with this catalyst were obtained at 100–110◦C for compound 3b.
The method could be used in the synthesis of other phosphorus deriva-
tives.
REFERENCES
[1] N. K. Roy and H. K. Taneja, J. Indian Chem. Soc., 69, 42 (1992).
[2] R. I. Tarasova, O. V. Voskresenskaya, K. V. Pinyangin, and V. V. Moskva, Zh. Prikl.
Khim., 63, 878 (1990).
[3] G. Ilia, A. Caprita, and G. Dehelean, Revue Roumaine de Chimie, 40, 391 (1995).
[4] R. Valceanu, G. Ilia, L. Kurunczi, and P. Soimu, Phosphorus, Sulfur and Silicon,
111, 642 (1996).
[5] G. Ilia, A. Caprita, R. Valceanu, and M. Tugui, Rev. Chim.-Bucharest, 47, 321 (1996).
[6] L. Mirci, J. Herdan, and G. Ilia, J. Synthetic Lubrication, 18, 115 (2001).
[7] A. Carayon-Gentil, Comp. Rend., 241, 1785 (1955).
[8] P. Chambrie and A. Carayon-Gentil, Bull. Soc. Chim. France, 639 (1957).
[9] R. Hazard, P. Chambrie, A. Carayon-Gentil, and Y. Fjevet, Comp. Rend., 240, 986
(1955).
[10] R. J. W. Cremlyn, J. David, and N. J. Kishore, Chem. Soc., Perkin Trans., 4, 583
(1972).
[11] I. K. Rubtsova and S. M. Shiner, Plasticheskie Masyy, 23 (1962).
[12] M. I. Kabachnik, T. Ya. Medved, I. M. Polikarpov, and K. S. Iudina, Dokl. Akad.
Nauk SSSR, Otd. Kim. Nauk, 1584 (1962).
[13] M. I. Kabachnik, T. Ya. Medved, I. M. Polikarpov, and K. S. Iudina, Dokl. Akad.
Nauk SSSR, Otd. Kim. Nauk, 2029 (1961).
[14] M. I. Kabachnik and T. Ya. Medved, Izv. Akad. Nauk SSSR, Ser. Kim., 1365 (1966).