Convenient one pot synthesis of phosphonites and H-phosphinates

Article abstract of DOI:10.1081/SCC-120018928

A convenient and simple one-pot method is described for the synthesis of phosphonites [RP(OEt)2, 1] and H-phosphinates [HP(O)R(OEt), 2] from triethyl phosphite and appropriate Grignard reagents.

Full text of DOI:10.1081/SCC-120018928

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Convenient One Pot Synthesis of Phosphonites and H-
Phosphinates
Imre Petneházy a , Zsuzsa M. Jászay b , Andrea Szabó a & Kinga Everaert a
a Department of Organic Chemical Technology, Budapest University of Technology and
Economics, Budapest, Hungary
b Organic Chemical Technological Research Group of the Hungarian Academy of Sciences,
Budapest, Hungary
Version of record first published: 17 Aug 2006.
To cite this article: Imre Petneházy, Zsuzsa M. Jászay, Andrea Szabó & Kinga Everaert (2003): Convenient One Pot Synthesis of
Phosphonites and H-Phosphinates, Synthetic Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 33:10, 1665-1674
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SYNTHETIC COMMUNICATIONSÕ
Vol. 33, No. 10, pp. 1665–1674, 2003
Convenient One Pot Synthesis of Phosphonites
and H-Phosphinates
2
1
Imre Petnehazy,1, Zsuzsa M. Jaszay, Andrea Szabo,
*
and Kinga Everaert1
1Department of Organic Chemical Technology,
Budapest University of Technology and Economics,
Budapest, Hungary
2Organic Chemical Technological Research Group of
the Hungarian Academy of Sciences,
Budapest, Hungary
ABSTRACT
A convenient and simple one-pot method is described for the
synthesis of phosphonites [RP(OEt)2, 1] and H-phosphinates
[HP(O)R(OEt), 2] from triethyl phosphite and appropriate
Grignard reagents.
*Correspondence: Imre Petnehazy, Department of Organic Chemical
Technology, Budapest University of Technology and Economics, H-1521
Budapest, P.O.Box 91, Hungary; Fax: 36-1-463-3648; E-mail: petnehazy.oct@
chem.bme.hu.
1665
DOI: 10.1081/SCC-120018928
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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1666
Petnehazy et al.
Key Words: Phosphonites; H-phosphinates; Grignard reaction.
Phosphonites (1) and H-phosphinates (2) are fundamental starting
compounds in P–C forming reactions such as in Michaelis–Arbuzov
reaction resulting in alkyl- and aryl phosphinates, in Kabachnik–Field
reaction resulting in a-aminophosphinates and in Abramov reaction
resulting in a-hydroxyphosphinates. The latter two have special attention
due to their ability to function as transition state analogue of carboxylic
acid moiety in natural a-amino- and a-hydroxycarboxylic acids.[1–3]
Despite the importance of 1 and 2 as precursors, there is no
convenient and simple method fortheirsynthesis so fa.r The methods
found in the literature are summarised in Sch. 1.
The oldest method forthe synthesis of 1 is the alcoholysis of dichloro
phosphinates[4] (3) (route a), the latter on the other hand can be prepared
in Kinnear–Perren reaction[5] by treating alkyl chlorides with phosphorus
trichloride (4) in the presence of aluminium–chloride and decomposing
the complex with a mixture of aluminium powder and sodium chloride in
reflux. The disadvantage of this procedure is that 3 is obtained only in very
low yield, especially in case of the preparation of the alkyl derivatives.
Other authors used Grignard-reagents such as alkyl-[6] orayrlzinc
halogenide[7] and dialkyl cadmium,[8] respectively in formation of P–C
bond starting also from phosphorus trichloride resulting in alkyl- and
Scheme 1.

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Synthesis of Phosphonites and H-Phosphinates
1667
aryldichloro phosphine (3) in very low yield. Although the chlorine
alkoxy exchange (route a) with different alcohols occurs in presence of
tertiary amines in suitable yield,[9] overall yield of the two steps is low and
because of the presence of some by-products difficult to purify.
Dialkyl phosphorous chloride (5) can also be reacted with reagents of
Grignard-type to give phosphonites (1) in medium yield (route b).[10]
However obtaining 5 in pure form is difficult, namely the alcoholysis of
phosphorus trichloride with two moles of alcohols results in a mixture of
mono-, di- and triesters. The other two routes leading to 5, i.e., the
chlorination of dialkyl phosphates[11] (6) and trialkyl phosphates[12] (7)
are also inconvenient and give low yield. The most promising method
for the preparation of phosphonites (1) and H-phosphinates (2) has been
reported by Sander.[13] According to this procedure (route c) triethyl
phosphite (7) is reacted with alkyl- or arylmagnesium bromide in diethyl
ether at room temperature, then the solvent is gradually changed to
benzene by removing the ether by distillation, because the completion
of the Grignard reaction needs higher temperature then that of the boil-
ing point of the ether. For production of 2 Sandersuggested hydrolysis of
1 by aqueous hydrochloric acid. To synthesize 1 in good yield and in high
quality the above mentioned methods were studied by us. Starting from
phosphorus trichloride (4) large amount of dialkyl phosphite (6), trialkyl
phosphite (7) and alkylphosphonates (8) were formed as by-products
beside phosphonite (1) by routes a and b, according to Sch. 1.
Starting from trialkyl phosphite (7) according to Sander’s procedure
(route c) we unexpectedly realized that the desired product (1) was pre-
sent only in a little amount compared to 2 and 8 by-products and the
unreacted 7 starting material, by the 31P-NMR spectra. We assumed that
the differences in results might be due to the fact that at the time of
Sander’s experiment the results could not be interpreted by 31P-NMR.
The reaction of the appropriate Grignard reagent and triethyl
phosphite (7, R2 ¼ Et) was optimized by us first aiming 1 and 2 (Sch. 2).
The ethyl esters of the phosphinous acids to be formed are more
Scheme 2.

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1668
Petnehazy et al.
favorable in their application as starting materials in subsequent synthesis
than theirhomologues.
We supposed that the reason of the side reactions was the heteroge-
neity of the reaction mixture in case of benzene as solvent. Therefore we
examined several solvents and mixture of solvents taking into considera-
tion their boiling points. Finally, tetrahydrofuran proved to be the best,
which resulted in homogenous reaction mixture, therefore the change of
solvent was not necessary. According to our experiments the optimum
reaction temperature was 50–55ꢀ and the application of tetrahydrofuran
was also advantageous in this point of view. We experienced that the
reaction does not occur on lower temperature namely in diethyl ether at
reflux, moreover oxidised by-products were also formed on elevated tem-
perature. The molar ratio of the Grignard reagent and triethyl phosphite
proved to be also substantial, we found that using a ratio of 1.5:1 provided
clean 1 and 2, adding the previously prepared Grignard compound into
the solution of triethyl phosphite in tetrahydrofuran at 50ꢀ.
The phosphinates (1) were isolated by distillation in vacuum simply
from the reaction mixture. For the preparation of 2 the hydrolysis was
performed by adding diluted hydrochloric acid directly into the concen-
trated reaction mixture of 1. The products were characterized by their
31P-NMR spectra, according to which in case of 1 three, in case of 2,
two types of the above mentioned contaminations could be observed only
in very low quantity (Tables 1 and 2).
We observed however, that using the trimethyl equivalent of 7
phosphinate 9 occurred as main product instead of required 1 (R2 ¼ Me).
We assume that 1 formed in the Grignard reaction is not stable,
Table 1. Isolated yield and boiling point of 1a–e and impurities by 31P-NMR data.
Product
RP(OEt)2
Impurities
1
P(OEt)3
7
HP(O)R(OEt) 2 RP(O)(OEt)2 8
Yield
Bp.
R
(%) (ꢀC/Hgmm)
Ratio in % (31P-NMR in ppm)
a
b
d
e
Et 50
Pr76
54–56/35
53–55/39
93 (185.6)
96 (184.9)
2.5 (140.8)
2.5
2.0 (40.6)
0 (38.4)
2.5 (33.4)
1.5 (34.9)
1.5 (35.0)
2.5 (21.4)
46.0 (35.0)
Bu 82
71–73/32
78–81/1
92.5 (185.1)
97 (158.0)
4.0
2.0 (38.9)
0 (26.5)
Ph 79
0.6
da Bu
19.7 (185.1)
20.0
15.3 (38.9)
aDistribution of products in reproduction of Sander’s procedure.

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Synthesis of Phosphonites and H-Phosphinates
1669
Table 2. Isolated yield and boiling point of 2a–e and impurities by 31P-NMR
data.
Product
B.p.
(ꢀC/Hgmm)
Impurities
RP(O)(OEt)2
Yield
(%)
8
R
HP(O)R(OEt) 2
% (ppm)
HP(O)(OEt)2 6
a
b
c
Et
56
78–80/10
88/10
97.5 (40.6)
2.3 (33.4)
1.9 (34.9)
0.2 (7.15)
0.1
b
)
Pr73
iPr84
Bu
98.0 (38.4
95.5 (43.9)
97.5 (38.9)
88–90/10
4.0 (34.7)
0.5
d
85
82
106/20
2.0 (35.0)
4.8 (21.4)
10.4 (35.0)
0.5
0.2
e
da
Ph
108–110/0.9
95.0 (26.5)
42.6 (38.9)
Bu
47
aDistribution of products in reproduction of Sander’s procedure.
bThere is a difference in 31P-NMR date given in literature[14,15] (see Experimental).
Scheme 3.
the methyl ester undergoes an Arbuzov fission in the reaction conditions
(Sch. 3).
In conclusion a simple one pot, high yielding modified procedure
was elaborated starting from triethyl phosphite (7 R ¼ Et) leading to
phosphonite 1 and H-phosphinate 2, though in case of 1a the yield is
lower. We observed that in case of trimethyl phosphite a further reaction
occurs resulting in phosphinate 9 in medium yield.
EXPERIMENTAL
1H-NMR and 13C-NMR spectra were recorded on a Bruker AC 250
instrument, 31P-NMR spectra on a Bruker DRX-500 instrument using
tetramethylsilane (1H, 13C) as internal standard and 85% H3PO4 (31P) as
external standard, all in CDCl3 solution. MS spectra were measured on a
Finnigan Automass GC/MS spectrometer.

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1670
Petnehazy et al.
General Procedure for Diethyl Alkyl
(or Aryl) Phosphonites (1)
Alkyl or aryl bromide (0.15 mol) was added dropwise to a mixture of
magnesium (3.6 g) and dry tetrahydrofuran (40 mL) under N2 atmo-
sphere at 50ꢀ. After addition, the reaction mixture was stirred at
50ꢀ for additional 1–2 h to complete the reaction. Then the mixture
is added dropwise to a solution of triethyl phosphite (0.1 mol, 16.6 g)
and THF (25 mL) between 40 and 50ꢀ in N2 atmosphere, then stirred
3 h at 50ꢀ. After removal the solvent under reduced pressure, the product
(1) was purified by distilled out from the semisolid residue in vacuum
(Table 1).
Diethyl ethylphosphonite (1a): Yield: 50%; b.p.: 54–56ꢀC/35 Hgmm
(lit.: 53ꢀC/30 Hgmm[13]); 1H-NMR ꢀ (ppm) ¼ 1.05 (dt, JHH ¼ 6.5 Hz,
JPH ¼ 14.3 Hz, 3H, CH3CH2P), 1.26 (t, JHH ¼ 7.1 Hz, 6H, CH3CH2O),
1.86 (dt, JHH ¼ 6.4 Hz, JPH ¼ 12.8 Hz, 2H, CH3CH2P), 3.72–3.97 (m,
JPH ¼ 12.1 Hz, 4H CH3CH2O); 31P-NMR: ꢀ (ppm) ¼ 185.6 (lit.: 186[16]
and 184[17]).
Diethyl propylphosphonite (1b): Yield: 76%; b.p.: 53–55ꢀC/39 Hgmm
(lit.: 52–53ꢀC/12 Hgmm[18]); H-NMR ꢀ (ppm) ¼ 0.99 (t, JHH ¼ 6.6 Hz,
1
3H, CH3CH2), 1.24 (t, JHH ¼ 7.0 Hz, 6H, CH3CH2O), 1.42–1.51 (m,
2H, CH3CH2), 1.85 (dt, JHH ¼ 6.6 Hz, JPH ¼ 12.0 Hz, 2H, CH2P),
3.70–3.91 (m, JPH ¼ 11.7 Hz, 4H, CH3CH2O); 13C-NMR:
ꢀ
(ppm) ¼ 15.08 (d, JPC ¼ 10.7 Hz, CH3CH2CH2), 15.29 (d, JPC ¼ 16.9 Hz,
CH3CH2CH2), 16.69 (d, JPC ¼ 5.5 Hz, CH3CH2O), 36.04 (d, JPC
¼
16.6 Hz, CH3CH2CH2), 62.15 (d, JPC ¼ 13.1 Hz, CH3CH2O); 31P-NMR:
ꢀ (ppm) ¼ 184.9.
Diethyl butylphosphonite (1d) Yield: 82%; b.p.: 71–73ꢀC/32 Hgmm
(lit.: 68.5–70ꢀC/12 Hgmm,[18] 39–40ꢀC/0.5 Hgmm[19]); 1H-NMR
ꢀ
(ppm) ¼ 0.92 (t, JHH ¼ 6.7 Hz, 3H, CH3CH2), 1.26 (t, JHH ¼ 7.1 Hz, 6H,
CH3CH2O), 1.28–1.37 (m, 2H, CH3CH2), 1.38–1.45 (m, 2H,
CH3CH2CH2), 1.45–1.60 (m, 2H,CH2P), 3.72–4.13 (m, JPH ¼ 15.0 Hz,
4H, CH3CH2O); 31P-NMR: ꢀ (ppm) ¼ 185.1.
Diethyl phenylphosphonite (1e): Yield: 79%; b.p.: 78–81ꢀC/1 Hgmm
(lit.: 74–78ꢀC/1 Hgmm,[20] 79–80ꢀC/1 Hgmm[21]); 1H-NMR ꢀ (ppm) ¼
1.28 (t, JHH ¼ 7.0 Hz, 6H, CH3CH2O), 3.80–3.96 (m, JHH ¼ 7.0 Hz, 4H,
CH3CH2O), 7.38–7.41 (m, 3H, ArH), 7.58–7.61 (m, 2H, ArH); ) (lit.[22] in
good accordance with our date); 13C-NMR ꢀ (ppm) ¼ 16.94 (d,
JPC ¼ 5.0 Hz, CH3CH2O), 62.27 (d, JPC ¼ 10.2 Hz, CH3CH2O), 127.97
(d, JPC ¼ 5.0 Hz, m-CH), 129.37 ( p-CH), 129.60 (d, JPC ¼ 10.1 Hz,
o-CH), 141.16 (d, JPC ¼ 19.6 Hz, C) (lit.[22] in good accordance with our
data); 31P-NMR: ꢀ (ppm) ¼ 158.0 (lit.: 155.9[23]).

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Synthesis of Phosphonites and H-Phosphinates
1671
General Procedure for Ethyl Alkyl
(or Aryl)-H-phosphinates (2)
The reaction mixture of 1 prepared according to the previous general
procedure was concentrated by distillation to the half in vacuum. Diluted
hydrochloric acid (1:1) was added to this stirred residue at room
temperature until pH ¼ 2. The solvent (tetrahydrofuran and water) was
evaporated and chloroform (60 mL) was added to the colourless, semi-
solid residue. The mixture was extracted with 3 Â 30 mL of water. The
organic phase was dried over Na2SO4. Afterevaporating the solvent, the
product was distilled in vacuum to give pure (2) (Table 2).
Ethyl ethyl-H-phosphinate (2a): Yield: 56%; b.p.: 78–80ꢀC/10 Hgmm
(lit.: 80–81ꢀC/16 Hgmm[24]); H-NMR ꢀ (ppm) ¼ 1.08 (dt, JHH ¼ 7.8 Hz,
1
JPH ¼ 21.2 Hz, 3H, CH3CH2P), 1.30 (t, J ¼ 7.0 Hz, 3H, CH3CH2O), 1.71
(qd, JHH ¼ 7.8 Hz, 2H, CH3CH2P), 4.05 (dq, JHH ¼ 7.0 Hz, 2H,
CH3CH2O), 6.97 (d, JPH ¼ 526.0 Hz, 1H, PH) (lit.[25] in good accordance
with ourdata); 13C-NMR: (ppm) ¼ 4.16 (d, JPC ¼ 3.9 Hz, CH3CH2),
15.76 (d, JPC ¼ 6 Hz, CH3CH2O), 21.27 (d, JPC ¼ 94.5 Hz, CH3CH2),
61.73 (d, JPC ¼ 6.8 Hz, CH3CH2O); 31P-NMR: ꢀ (ppm) ¼ 40.6 (lit.:
38[26] and 40[27]); MS (m/z): 93 ([EtPO2H]þ, 1%), 78 ((EtPOH2]þ,
32%), 65 ([PO2H2]þ, 100), 47 ([PO]þ, 67%).
Ethyl propyl-H-phosphinate (2b): Yield: 73%; b.p.: 88ꢀC/10 Hgmm;
1H-NMR ꢀ (ppm) ¼ 1.05 (t, JHH ¼ 7.0 Hz, 3H, CH3CH2CH2), 1.36
(t, JHH ¼ 7.0 Hz, 3H, CH3CH2O), 1.55–1.83 (m, 4H, CH3CH2CH2),
3.99–4.14 (m, 2H, CH3CH2O), 7.04 (d, JPH ¼ 524.0 Hz, 1H, PH);
13C-NMR: ꢀ (ppm) ¼ 14.40 (d, JPC ¼ 2.6 Hz, CH3CH2CH2), 14.86
(d, JPC ¼ 16 Hz, CH3CH2O), 16.02 (d, JPC ¼ 6 Hz, CH3CH2CH2), 30.47
(d, JPC ¼ 93.6 Hz, CH3CH2CH2), 62.05 (d, JPC ¼ 7 Hz, CH3CH2O);
31P-NMR: ꢀ (ppm) ¼ 38.4 (lit.: 26.9 ppm,[14] 23.5 ppm[15]); MS (m/z): 136
([M]þ, 1%), 121 ([CH2CH2PO2EtH]þ, 2%), 108 ([CH2PO2EtH]þ, 3%),
93 ((EtPO2H(þ, 26%), 80 ([CH2PO2H]þ, 34%), 65 ([PO2H2]þ, 100%).
Ethyl isopropyl-H-phosphinate (2c): Yield: 84%; b.p.: 88–90ꢀC/
10 Hgmm; 1H-NMR ꢀ (ppm) ¼ 1.14 (d, JHH ¼ 7.23 Hz, 3H), 1.22
(d, JHH ¼ 7.23 Hz, 3H) CH3CH3CH, 1.37 (t, JHH ¼ 7.0 Hz, 3H,
CH3CH2), 1.85–1.94 (m, 1H CH3CH3CH), 4.00–4.22 (m, 2H,
CH3CH2), 6.88 (d, JPH ¼ 518.3 Hz, 1H, PH); 31P-NMR: ꢀ (ppm) ¼ 43.9.
Ethyl butyl-H-phosphinate (2d): Yield: 85%; b.p.: 106ꢀC/20 Hgmm
(lit.: 105ꢀC/15 Hgmm[13]); 1H-NMR ꢀ (ppm) ¼ 0.84 (t, JHH ¼ 7.1 Hz,
3H, CH3CH2CH2CH2), 1.27 (t, J ¼ 7.1 Hz, 3H, CH3CH2O), 1.32–1.75
(m, 6H, CH3CH2CH2CH2), 3.97–4.11 (m, 2H, CH3CH2O), 6.99 (d,
JPH ¼ 528.8 Hz, 1H, PH) (lit.[28] in good accordance with our data);
13C-NMR: ꢀ (ppm) ¼ 13.40 (s, CH3CH2CH2CH2), 16.11 (d, JPC ¼ 6 Hz,

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1672Petneha
zy et al.
CH3CH2O), 22.59 (d, JPC ¼ 2.5 Hz, CH3CH2CH2CH2), 23.39 (d, JPC
¼
16.2 Hz, CH3CH2CH2CH2), 28.29 (d, JPC ¼ 93.7 Hz, CH3CH2CH2CH2),
62.08 (d, JPC ¼ 6.9 Hz, CH3CH2O); 31P-NMR: ꢀ (ppm) ¼ 38.9; MS (m/z):
121 ([CH2CH2PO2EtH]þ, 4%), 108 (37%), 93 ([EtPO2H]þ, 35%), 80
([CH2PO2H]þ, 89%), 65 ([PO2H2]þ, 100%).
Ethyl phenyl-H-phosphinate (2e)Yield: 82%; b.p.: 108–110ꢀC/
0.9 Hgmm (lit.: 95ꢀC/1 Hgmm[29]); 1H-NMR
ꢀ
(ppm) ¼ 1.37 (t,
J ¼ 7.2 Hz, 3H, CH3CH2O), 4.14 (m, 2H, CH3CH2O), 7.58 (d,
JPH ¼ 562.79 Hz, 1H, PH), 7.48–7.57 (m, 3H, ArH), 7.61–7.83 (m, 3H,
ArH) (lit.[30] in good accordance with our data); 13C-NMR
ꢀ
(ppm) ¼ 16.07 (d, JPC ¼ 6.3 Hz, CH3CH2O), 61.76 (d, JPC ¼ 6.3 Hz,
CH3CH2O), 128.47 (d, JPC ¼ 13.83 Hz, m-CH), 129.51 (d, JPC ¼ 98.49 Hz,
C), 130.59 (d, JPC ¼ 11.95 Hz, o-CH), 132.81 (d, JPC ¼ 3.14 Hz, p-CH);
31P-NMR: ꢀ (ppm) ¼ 26.5 (lit.: 23.5[29]); MS (m/z): 171 ([M]þ, 1%), 142
([PhPO2H]þ, 1%), 78 ((EtPOH2]þ, 11%), 65 ([PO2H2]þ, 8%), 47
([PO]þ, 100%).
Methyl methyl-propylphosphinite (9b): It was prepared in a similar
way as (2) except trimethyl phosphite (0.1 mol, 12.4 g) was used instead
of triethyl phosphite. Yield: 43%; b.p.: 98–99ꢀC/14 Hgmm; H-NMR ꢀ
1
(ppm) ¼ 1.04 (t, J
¼ 6.8 Hz, 3H, CH2CH3), 1.45 (d, JPH ¼ 13 Hz, 3H,
HH
PCH3), 1.5–1.8 (m, 4H, CH2), 3.7 (d, JPH ¼ 10.7 Hz, 3H, OCH3);
13C-NMR (CDCl3): ꢀ ¼ 12.9 (d, JPC ¼ 90 Hz, PCH3), 15.5 (d, JPC ¼ 30 Hz,
CH2CH3), 15.6 (d, JPC ¼ 10 Hz, CH2CH2CH3), 31.2 (d, JPC ¼ 94 Hz,
PCH2), 50.6 (d, JPC ¼ 7 Hz, OCH3); 31P-NMP: ꢀ (ppm) ¼ 58.2.
ACKNOWLEDGMENTS
Support from the Hungarian National Research Foundation (OTKA
T026478) and the Ministry of Education (TET-Balaton F19/98) is
acknowledged.
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Synthesis of Phosphonites and H-Phosphinates
1673
3. (a) Bagrov, F.V.; Abramova, M.V.; Kiselev, V.I. J. Gen. Chem. USSR
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Received in the UK April 10, 2002