A convenient synthesis of primary 2-hydroxyorganophosphines from red phosphorus and oxiranes

Article abstract of DOI:10.1055/s-2000-6238

A number of 2-hydroxyorganophosphines HOCH(R¹)CH(R²)PH₂ 2 have been obtained in good yields by reaction of oxiranes with sodium monophosphide, generated in situ from red phosphorus, sodium and tert-butyl alcohol in liquid

Full text of DOI:10.1055/s-2000-6238

SHORT PAPER
65
A Convenient Synthesis of Primary 2-Hydroxyorganophosphines from Red
Phosphorus and Oxiranes
S. N. Arbuzova,*a L. Brandsma,b N. K. Gusarova,a A. H. T. M. van der Kerk,b M. C. J. M. van Hooijdonk,b B. A.
Trofimova
a Irkutsk Institute of Chemistry of the Russian Academy of Sciences, Siberian Branch, Favorsky Street 1, 664033, Irkutsk, Russia
E-mail: arbuzova@irioch.irk.ru
b Department of Preparative Organic Chemistry of the Utrecht University, Padualaan 8, NL-3584 CH Utrecht, The Netherlands
E-mail: L.brandsma@chem.ruu.nl
Received 7 July 1999; revised 13 July 1999
Abstract:
A
number
of
2-hydroxyorganophosphines
HOCH(R1)CH(R2)PH2 2 have been obtained in good yields by re-
action of oxiranes with sodium monophosphide, generated in situ
from red phosphorus, sodium and tert-butyl alcohol in liquid am-
monia.
Key words: phosphines, oxiranes, ring opening, phosphorus, sodi-
um, liquid ammonia
Orientation of ring opening in the case of monosubstituted
oxiranes 1b,c is in agreement with Krassusky’s rule:5
phosphide-anion attacks the less substituted carbon atom
to result in secondary alcohols.
Primary 2-hydroxyorganophosphines, being amphiphilic
compounds with polar hydrophilic functions and hydro-
phobic branched counterparts, can be prospective ligands
for design of metallocomplex catalysts combining proper-
ties of phase transfer and micellar catalysts. They were
1H spectra were recorded on a Bruker AC 300 (300 MHz) (for
1a,b,d) or Varian EM-390 (90 MHz) (for 1c) spectrometers using
TMS as internal standard. 31P spectra were taken on a Bruker AC
synthesized earlier from hazardous phosphines and ox- 300 instrument (121.5 MHz). Mass spectra were recorded on a Jeol
iranes in the system sodium/liquid ammonia.1 It is also
AX-505 at 70 eV. All operations were carried out under N2.
known that reaction of white2 or red3 phosphorus with ox-
2-Hydroxyorganophosphines 2a–c; General Procedure
To anhyd liquid ammonia (1.5 L), a slurry of red phosphorus (6.2 g,
0.2 mol) in anhyd THF (20 mL) was introduced, followed by addi-
tion of sodium (16.6 g, 0.72 mol), freshly cut into pieces of 0.2–0.4
iranes in the presence of bases (alkali metal hydroxides or
alkoxides, amines) and proton donors (water, alcohols)
gives phosphorus-containing polyols.
g, over 10 min. A mixture of t-BuOH (38.5 g, 0.52 mol) and Et2O
(40 mL) or THF was then added dropwise over 1 h with very effi-
cient stirring. The mixture was stirred until the blue colour had dis-
appeared and a yellowish suspension formed. To the suspension, an
oxirane 1a–c (0.32 mol) was added in 5–7 min and the mixture was
stirred for 40 min. Then NH4Cl (20.0 g) was introduced and the
mixture was stirred for an additional 30 min. The ammonia was
The present communication deals with an efficient meth-
od for preparing primary 2-hydroxyorganophosphines 2
by the direct interaction of oxiranes 1 with red phosphorus
in the system sodium/tert-butyl alcohol/liquid ammonia.
In this system, with the stoichiometry shown in the
Scheme, sodium monophosphide is generated4 to furnish,
upon treatment with oxirane followed by a proton donor evaporated at ~40°C. To the residue, 200 mL of a solvent (CH2Cl2,
CHCl3 and Et2O were used for 2a, 2b and 2c, respectively) and H2O
addition, phosphines 2 in 60–70% yields (Table).
(500 mL) were successively added. After vigorous stirring, the lay-
ers were separated, followed by extraction with the solvent (3 × 150
mL). The combined organic extracts were dried (MgSO4), the sol-
vent and excess oxirane 1 were removed in a water pump vacuum,
and the remaining liquid was distilled in vacuo through a 25–30 cm
Vigreux column (Table). Phosphine 2c decomposes so rapidly upon
exposure to air, that combustion or even explosion can occur, sty-
rene being identified among the decomposition products. Care must
be taken also during evaporation of the solvent and distillation of
the product, addition of a little amount of Et3N was used to prevent
explosion.
2-Hydroxycyclohexylphosphine (2d)
A suspension of NaPH2 was prepared in a similar way as described
above. Then ammonia was evaporated at ~40°C, DMSO (100 mL)
introduced and 1d (0.32 mol) added in 5–7 min. The mixture was
stirred at 65–70°C for 1 h, cooled to r.t., diluted with H2O (500 mL),
after which extractions with Et2O (3 × 150 mL) were carried out.
The combined ethereal extracts were washed with H2O (3 × 100
Unlike the oxiranes 1a–c, which react smoothly with so-
dium monophosphide in liquid ammonia, 7-oxabicyc-
lo[4.1.0]heptane (1d) turned out to be less reactive, and
the reaction with it occurred only in dimethyl sulfoxide
(Table).
Synthesis 2000, No. 1, 65–66 ISSN 0039-7881 © Thieme Stuttgart · New York

66
S. N. Arbuzova et al.
SHORT PAPER
Table Hydroxyorganophosphines 2 Prepared
Product
R1
H
R2
H
Yielda
(%)
bp
1H, 31P NMR (CDCl3)b
δ, J (Hz)
MS (EI), m/z (%)c
(oC/Torr)
2a
68
50–53/20d
3.69 (m, 2 H, CH2OH), 2.47 (dm,
2 H, 1JH,P = 196, H2P), 1.74 (m, 2
H, CH2P),
78 (M+, 4), 60 (M+ – H2O,
100), 58 (46), 45
+
(HOCH2CH2 , 35), 31
+
–154.8
(HOCH2 , 27), 27 (12), 19 (3),
18 (2)
2b
Me
H
H
67
62–65/20e
3.87 (sept, 1 H, 3JCH,P = 6.1, 3J
(CH,CH2) = 6.1, 3J (CH,CH3) =
6.1, CHOH), 2.67 (dm, 2 H, 1JH,P
= 196, H2P), 2.92 (br s, 1 H, OH),
1.73 (m, 2 H, CH2P), 1.26 (d, J =
6.1, 3 H, CH3),
92 (M+, 1.8), 91 (M+ – H, 1.3),
74 (M+ – H2O, 100), 57 (12), 48
+
(CH3PH2 , 42), 45
(CH3CHOH+, 86), 41 (24), 31
(14), 28 (13), 27 (11), 19 (4),
18 (2)
–155.0
2c
Ph
60
70
125–130/20
95–100/20
7.3 (m, 5 H, C6H5), 4.6 (m, 1 H,
CHOH), 1.9 (m, 2H, CH2P),
–154.7 (1JH,P = 197)
_
2df
(CH2)4
3.28 (m, 1 H, CHOH), 3.02 (br s,
1 H, OH), 2.81, 2.71 (AB part of
doublet ABX system, 1 H each,
132 (M+, 2), 114 (M+ – H2O,
64), 98 (M+ – PH3, 7), 81 (cyc-
+
lo-C6H9 , 100), 67 (18), 55
1JH,P = 197, 2JA,B = 12.1, 3JA,X
=
(19), 41 (23), 28 (12), 27 (8),
18 (2)
5.2, 3JB,X = 6.4, PH2), 2.1–1.2 (m,
9 H overall, CHP, CH2),
–127.3
a Yield based on phosphorus used.
b 31P NMR values are given in italics.
c HRMS for 2a: C2H7OP, m/z Calcd.: 78.0235, Found: 78.0180; 2b: C3H9OP, Calcd.: 92.0391, Found: 92.0462; 2d: C6H13OP,
Calcd.: 132.0704, Found: 132.0665.
d Lit1a bp 139-140oC/760 Torr.
e Lit1a bp 37-39oC/2 Torr.
f Purity ~ 90% (GC, 1H NMR).
(b) Ivanov, B.E.; Fridland, N.S.; Abul’khanov, A.G.;
Krokhina, S.S.; Ilyasov, A.V. Izv. Akad. Nauk. USSR, Ser.
Khim. 1987, 1399; Chem. Abstr. 1988, 109, 23033.
(c) Fridland, N.S.; Ivanov, B.E.; Krokhina, S.S.;
Abul’khanov, A.G. Izv. Akad. Nauk. USSR, Ser. Khim. 1988,
710; Chem. Abstr. 1988, 109, 211554.
mL), dried (MgSO4), the solvent and excess 1d were removed in a
water pump vacuum, and the remaining liquid was distilled in vacuo
through a 25–30 cm Vigreux column (Table).
Acknowledgement
(3) Gusarova, N.K.; Trofimov, B.A.; Khilko, M.Ya.; Malysheva,
S.F.; Rakhmatulina, T.N.; Nedolya, N.A. Zh. Obshch. Khim.
1990, 60, 1925; Chem. Abstr. 1991, 114, 42941.
(4) Trofimov, B.A.; Gusarova, N. ; Brandsma, L. MGCN, Main
Group Chemistry News 1996, 4, 18; Chem. Abstr. 1996, 125,
142810.
(5) (a) Krassusky, K. J. Prakt. Chem. 1907, 75, 238.
(b) Krassusky, K. Compt. Rend. 1908, 146, 236.
(c) Parker, R.E.; Isaaks, N.S. Chem. Rev. 1959, 59, 737.
The financial support of the Shell (Amsterdam) and Russian Fund
of Fundamental Research (Grant No. 99-03-32939) is gratefully
acknowledged.
References
(1) (a) Knunyants, I.L.; Sterlin, R.N. Dokl. Akad. Nauk. USSR.
1947, 66, 47; Chem. Abstr. 1948, 42, 519.
(b) Perveev, F.Ya.; Rikhter, K. Zh. Obshch. Khim. 1960, 30,
784; Chem. Abstr. 1961, 55, 1580.
(2) (a) Boros, E.J.; Lanham, W.M.; Chisung, W. Ind. Eng. Chem.
Prod. Res. Dev. 1973, 12, 221.
Article Identifier:
1437-210X,E;2000,0,01,0065,0066,ftx,en;Z05199SS.pdf
Synthesis 2000, No. 1, 65–66 ISSN 0039-7881 © Thieme Stuttgart · New York