Reaction of 1-bromonaphthalene with PH3 in the t-BuOK/DMSO system: PCl3-free synthesis of di(1-naphthyl)phosphine and its oxide

Article abstract of DOI:10.1016/j.tet.2017.06.036

The phosphine, generated together with hydrogen from red phosphorus and aqueous KOH, reacts with 1-bromonaphthalene in the t-BuOK/DMSO system under mild conditions (70 °C, atmospheric pressure) to give di(1-naphthyl)phosphine, which is easily oxidized in the presence of air to afford di(1-naphthyl)phosphine oxide in 45% preparative yield. Tri(1-naphthyl)phosphine and naphthalene are also formed in the reaction in 23 and 27% yield, respectively. According to ESR and UV data, the studied phosphination of 1-bromonaphthalene involves a single electron transfer process.

Full text of DOI:10.1016/j.tet.2017.06.036

Accepted Manuscript
Reaction of 1-bromonaphthalene with PH in the t-BuOK/DMSO system: PCl -free
3
3
synthesis of di(1-naphthyl)phosphine and its oxide
Vladimir A. Kuimov, Elena A. Matveeva, Spartak S. Khutsishvili, Tamara I.
Vakul'skaya, Lidiya M. Sinegovskaya, Svetlana F. Malysheva, Nina K. Gusarova,
Boris A. Trofimov
PII:
S0040-4020(17)30669-5
10.1016/j.tet.2017.06.036
TET 28801
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 8 February 2017
Revised Date: 6 June 2017
Accepted Date: 19 June 2017
Please cite this article as: Kuimov VA, Matveeva EA, Khutsishvili SS, Vakul'skaya TI, Sinegovskaya LM,
Malysheva SF, Gusarova NK, Trofimov BA, Reaction of 1-bromonaphthalene with PH in the t-BuOK/
3
DMSO system: PCl -free synthesis of di(1-naphthyl)phosphine and its oxide, Tetrahedron (2017), doi:
3
10.1016/j.tet.2017.06.036.
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Reaction of 1-bromonaphthalene with PH3 in the
t-BuOK/DMSO system: PCl3-free synthesis of
di(1-naphthyl)phosphine and its oxide
Leave this area blank for abstract info.
Vladimir A. Kuimova, Elena A. Matveevaa, Spartak S.
work-up
air
Khutsishvilia, Tamara I. Vakul’skayaa, Lidiya M.
PH3/H2
Sinegovskayaa, Svetlana F. Malyshevaa, Nina K.
Gusarovaa, Boris A. Trofimova
O
P
Br
H
+
P
Pred
aq.KOH
t-BuOK/DMSO
+

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Reaction of 1-bromonaphthalene with PH3 in the t-BuOK/DMSO system: PCl3-free
synthesis of di(1-naphthyl)phosphine and its oxide
Vladimir A. Kuimova , Elena A. Matveevaa, Spartak S. Khutsishvili a, Tamara I. Vakul’skayaa, Lidiya M.
Sinegovskayaa, Svetlana F. Malyshevaa, Nina K. Gusarovaa Boris A. Trofimova
,
a A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk, Russian Federation
ARTICLE INFO
ABSTRACT
Article history:
Received
The phosphine, generated together with hydrogen from red phosphorus and aqueous KOH,
reacts with 1-bromonaphthalene in the t-BuOK/DMSO system under mild conditions (70 C,
o
Received in revised form
Accepted
Available online
atmospheric pressure) to give di(1-naphthyl)phosphine, which is easily oxidized in the presence
of air to afford di(1-naphthyl)phosphine oxide in 45% preparative yield. Tri(1-
naphthyl)phosphine and naphthalene are also formed in the reaction in 23 and 27% yield,
respectively. According to ESR and UV data, the studied phosphination of 1-bromonaphthalene
involves a single electron transfer process.
Keywords:
1-Bromonaphthalene
Phosphine
2017 Elsevier Ltd. All rights reserved
.
Superbase System
Di(1-naphthyl)phosphine
Di(1-naphthyl)phosphine oxide
Single electron transfer
———
Corresponding author. Tel.: +0-000-000-0000; fax: +0-000-000-0000; e-mail: author@university.edu

2
Tetrahedron
TfONp) via palladium-catalyzed cross-coupling.20 Recently, we
ACCEPTED MANUSCRIPT
have reported21 a simple and straightforward synthesis of tri(1-
1. Introduction
naphthyl)phosphine by the direct phosphination of 1-
bromonaphthalene with red phosphorus in a KOH/DMSO
Organic phosphines and phosphine oxides, bearing sterically
hindered substituents, for instance, naphthyl moieties, are
excellent ligands for metal complex catalysts inducing many
types of transformations.1 So, di(1-naphthyl)phosphine and its
oxide are of special importance as a building block for the
construction of luminescent materials,2 bidentate,3 asymmetric4
and special tripod-ligands.5 The latter are used as catalysts and
co-catalysts for asymmetric hydrogenation,6 hydroformylation,7
alkylation,8 Diels-Adler5b reaction as well as for alkene
polymerization.9 In addition, di(1-naphthyl)phosphine oxide was
suspension
(Scheme
2).
No
formation
of
di(1-
naphthyl)phosphine has been observed under the studied
condition.
The data on the reaction of 1-bromonaphthalene with
phosphine are lacking in the literature. Meanhile, 1-
bromonaphthalene is known to react with t-BuOK/DMSO to give
naphthalene,
1-
and
1-
dinaphthyl
2-methylnaphthalenes,
and 2-tert-butoxynaphthalenes,
ethers, naphthols,
1,2-
dimethylnaphthalene,
dinaphthalenes,
claimed as
a
stabilizer of nanoparticles.10 Tri(1-
methylmercaptonaphthols.22
naphthyl)phosphine, in its turn, was employed for the preparation
of complexes11 showing high catalytic activity in the cross-
coupling reactions,12 synthesis of diaryl ketones13 and alcohols,14
hydrogenation,15 cyclization,16 and reduction reaction17 as well as
the complexes having intense long-lived luminescence and
photoluminescence.11a,f
However,
the
traditional
syntheses
of
bulky
naphthylphosphines, including di(1-naphthyl)phosphine and its
oxide, are multistep, laborious and require highly aggressive
phosphorus halogenides and flammable organometallic
reactants.4c,7,18 For example, these reactions typically involve
either PCl3/n-BuLi (or Grignard) reagents (Scheme 1a,b) or
cleavage of tri(1-naphthyl)phosphine by alkali metals (Scheme
1b). Herein, we describe the convenient synthesis of di(1-
naphthyl)phosphine and its oxide from 1-bromonaphthalene and
phosphine in the t-BuOK/DMSO system (Scheme 1c). Phosphine
is an industrial tail gas19 and can serve as a cheap source of P,
thus search for its utilization is highly desirable. In this work,
phosphine is generated together with hydrogen from red
phosphorus and aqueous KOH (60%) and used further without
isolation and purification. It is worth emphasizing that PH3/H2
mixture proved to be easily handled by using a common glass
flask placed under a fume hood. Important, that PH3/H2 is
generated and directed to the reaction mixture only on demand,
i.e. in a dosed flow, which is immediately stopped after the
reaction completion that warrants sufficient safety (see
Supporting information Scheme S1 and Pic. 1).
Scheme 2. Synthesis of tri(1-naphthyl)phosphine from red
phosphorus and 1-bromonaphthalene
2. RESULTS AND DISCUSSION
Our experiments have showed that phosphine reacts with 1-
bromonaphthalene (BrNp) under the action of the superbase
catalytic system such as t-BuOK/DMSO, t-BuONa/DMSO and
o
KOH/DMSO at heating (60‒80 C, 2.5‒6 h, argon blanket) to
afford di(1-naphthyl)phosphine 1-Np2PH, which is selectively
oxidized in the process of its isolation on air to produce di(1-
naphthyl)phosphine oxide, 1-Np2P(O)H. Under the studied
conditions, tri(1-naphthyl)phosphine 1-Np3P and naphthalene
NpH are also formed (Table 1). It is worthwhile to note that
BrNp is slowly added dropwise to the PH3/t-BuOK/DMSO
system to avoid exhaustive phosphine arylation. Moderate yields
of 1-Np2PH (up to 45%) are attained using the superbase system
t-BuOK/DMSO and heating of the reagents at 60‒70 °C for 2.5‒
4
h (Table 1, entries 1-3). In these experiments, 1-
naphthylphosphine oxide 1-NpP(O)H2, 1,2-dinaphthylphosphine
1,2-Np2PH and 1,1,2-trinaphthylphosphine 1,1,2-Np3P are
detected in small amounts (NMR data, see Supporting
o
information, Scheme S2). At a higher temperature (80 C), the
yield of phosphines 1,2-Np2PH, 1,1,2-Np3P and 1,2,2-Np3P
slightly increases (~5-10%). Under these conditions, the
formation of polynaphthalenes are also observed (Table 1, entry
4, see also Supporting information). The latters are also formed
when the superbase t-BuONa/DMSO system is used (Table 1,
entries 5, 6).
Notably, the target 1-Np2P(O)H is easily oxidized with
o
oxygen (air) at heating (50‒70 C) in organic solvents to afford
practically quantitatively di(1-naphthyl)phosphinic acid, an
effective ligand and building block in organic chemistry4f,h,8b,23
(Scheme 3).
Scheme 1. Synthesis of di(1-naphthyl)phosphine and its oxide
Also, J.-L. Montchamp and co-workers have synthesized
organophosphorus derivatives of naphthalene without PCl3 from
available reagents (anilinium hypophosphite and BrNp or

3
Scheme 3. Oxidation of di(1-naphthyl)phosphine oxide
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Table 1
Optimization of the reaction conditions.a
Products (yield %)b
Conversion of
BrNp (%)
Entry
Base
Temp (oC)
Time (h)
1-Np2P(O)H
1-Np3P
23
NpH
27
1
2
t-BuOK/DMSO
t-BuOK/DMSO
t-BuOK/DMSO
t-BuOK/DMSO
t-BuONa/DMSO
t-BuONa/DMSO
KOH/DMSO
70
60
4
4
45
35
39
19
38
35
4
91
86
90
99
99
88
53
30
86
9.3
4
19
3c
4de
5e
6e
7
65‒70
80
2.5
4
32
26
23
60
6
16
9.2
28
70
2.5
4
8.4
2.5
1.5
7
65‒70
60
28
8
9f
KOH/DMSO
5
0
23
t-BuOK/DMSO
60
2.5
7
27
a
The reaction conditions for entries 1-6, 9: BrNp (48.3 mmol), t-BuOK or t-BuONa (72.5 mmol), DMSO (80 mL);
for 7 and 8 entries: BrNp (48.3 mmol), KOH (178.5 mmol), DMSO (40-50 mL).
b The yield was calculated on the basis of BrNp consumed.
c 120 mL DMSO was used.
d The structural isomers of phosphines were also formed.
e The large amounts of insoluble polynaphthalenes were formed.
f TEMPO (10 mol%) was added.
The system PH3/KOH/DMSO appears to be ineffective for
phosphination of BrNp, the other conditions being the same
(entries 7 and 8). This is likely due to extremely poor solubility
of КОН in DMSO (13 mg/100 mL DMSO)24 that leads to low
concentration of phosphide-anion (¯ PH2). Therefore, the reaction
of PH3 with naphthalene radical furnishes naphthalene owing to
abstraction of hydrogen atom. In that case, naphthalene becomes
the major reaction product (Scheme 4, path A).
Scheme 4 Two ways of interactions naphthalene radical with PH3 in different superbasic systems.
In the case of homogeneous system t-BuOK/DMSO (entries
1-6), phosphine (PH3) is almost completely ionized to the
phosphide anion (¯ PH2), which is able to add to more
electrophilic 1-naphthyl radical to furnish the anion-radical of 1-
naphthylphosphine (Scheme 4, path B). Abstraction of hydrogen
atom from the solvent by 1-naphthyl radicals gives the reduction
product, naphthalene. At a lower temperature (60 oC, entry 2), the
yield of Np2PH notably drops, although at a higher temperature
(80 oC) Np3P starts to be prevalent (entry 4). The prolonged
process time does not provide higher yields of the target
products. Comparison of the three reaction conditions indicates
that the new procedure (t-BuОК/DMSO) is far superior to the
method involving KOH or t-BuОNa/DMSO in terms of the
application scope and the product yield. Then we have found that
the reaction is inhibited by the addition (10 mol%) of the radical
scavenger TEMPO (entry 9), as well as does not occurs in the
absence of a base. These facts suggest ion-radical mechanism of
the reaction. This assumption is also confirmed by ESR and UV
spectra of the reaction mixture (vide infra).
Actually, as shown in21, the reaction proceeds through radical
nucleophilic substitution (SRN1-mechanism25). The proposed
base-promoted SRN1-mechanism is a chain process involving
radicals and radical anions as intermediates (Scheme 5). The
initiation step is an electron transfer (SET) from H2Pꢀ anion to
BrNp to yield an [BrNp]ꜙ radical anion, which then fragments to
produce a naphthyl radical [Np]˙ and an bromine ion (Brꢀ). The
[Np]˙ formed is able of coupling with H2Pꢀ anion to give radical
anion [NpPH2]ꜙ, which reacts as an electron transfer reagent to
give the primary phosphine NpPH2, coupling product after ET to

4
Tetrahedron
the radical precursor, and these cycles repeats again one or two
with participation of 1-naphthylphosphide anion (NpHPꢀ) giving
ACCEPTED MANUSCRIPT
times to eventually give Np2PH or Np3P.
radical NpHP˙, which is detected by ESR with spin-trapping
technique, together with naphthyl radical (depicted in Scheme 5
in red).
It is interesting to note that recombination of the radicals does
not lead to the reaction quenching, since the ET process proceeds
Scheme 5. Proposed mechanism of Np2PH synthesis (depicted in green)
The reaction was studied by ESR techniques both in
It should be emphasized that usually SRN1 mechanism is
КОН/DMSO and t-BuOK/DMSO media (see ESI). An attempt to
directly detect phosphorus-centered and free naphthalene radicals
in the reaction mixture using ESR method failed due to their
extremely low stability.26 Therefore, the reaction was carried out
in the presence of spin trap, С-phenyl-N-tert-butylnitrone
(PBN)27, directly in resonator of the ESR spectrometer. The
recorded spectrum (Fig. 1a, top left) was simulated (Fig. 1b,
bottom left) to demonstrate that it contains the overlapped signals
of three spin adducts I-III (Fig. 2), two doublet triplets with an
intensity ratio of ~ 10:1: I) g = 2.0077, aN = 14.58 G, aH = 4.23 G;
II) g = 2.0077, aN =15.80 G, aH = 2.30 G and III) weak nitrogen
triplet (aN =14.60 G) split into 3 doublets with the following
constants aP = 15.00 G, aH = 4.8 G, aH = 2.6 G with g = 2.0080.
The latter signal disappears by the end of the reaction, and the
spectrum contains only two the above doublet triplets.
Noteworthy, the initial ratio of these signals changes and
becomes approximately equals, while the total intensity decreases
(Fig. 1c top right). The first two signals are assigned to spin
adducts of naphthalene carbon-centered radicals, which differ by
constants of hyperfine coupling (HFC), and third signal is
attributed to spin adducts of the trap with phosphorus-centered
radical NpHP˙ (see Scheme 5).
triggered by photo- or electrochemical activation,25b,c,d but in our
case the thermally initiated SRN1 reaction is observed since it
occurs even in the dark27. Curiously enough, the expected
intermediate primary phosphine in the reaction mixture is
detected in about 1-5%, probably because of easy dissociation of
1-naphthylphosphine to the corresponding anion and it
participation in SET to the BrNp.
Surprisingly, the competitive C-H arylation of BrNp with
naphthyl radical, known as BHAS (base-promoted homolytic
aromatic substitution) reaction, typical for unactivated aromatic
rings25e,28 (Scheme S3), represents a minor process. The direct
cross-coupling products BrNpNp or binaphthyls have been
detected in the reaction mixtures in an amount of 5-7%
(identified in the reaction mixture by MS).
Following this mechanism the naphthalene radical turns out to
react with 1-halonaphthalene to furnish 4-halo-1,1’-
binaphthalene.28c To suppress this process, one should dilute the
reaction mixture to increase concentration of the phosphide-
anions (H2Pꢀ) and to slow the addition of BrNp. However, it is
worth noting that a larger amount of DMSO gives lower yields
due to H-abstraction (Table 1, entry 4). ˙

5
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Figure 1. ESR spectra of the reaction mixture PH3/KOH/DMSO/ PBN: left – experimental (top) – in 30 min after the reaction beginning, simulated (bottom);
right – experimental (top) - in 2 h, simulated (bottom).
BuO·]K+, solvated by DMSO (Scheme 6). The band at 408 nm
rather quickly disappears (for 1-2 min), whereas the band at 540
nm is stable for a long time (1-4 h in Ar atmosphere, more details
see ESI). In our earlier works,29 in the reaction of primary or
secondary phosphines with acetylenes we have observed charge-
transfer absorption band at 412 and 454 nm, attributed to some
radical species formed via SET.
Figure 2. Spin adducts
To shed a further light on the possible reaction mechanism, we
have recorded the UV-Vis spectra of the reaction mixture under
an Ar atmosphere. We have revealed that t-BuOK is dissolved in
DMSO forming a pale-yellowish solution, a band being observed
at 307 nm (Fig.3). Coloring of the solution likely indicates the
generation of solvate-separated ionic pair of the type
K+ꢁꢁꢁO→S+Me2ꢁꢁꢁꢀOt-Bu. The addition of phosphine (PH3) to this
mixture results in a new band at 364 nm, which could be
assigned to complexes involving phosphide-anion. The
introduction of 1-bromonaphthalene leads to deep dark-purple
coloring and appearance of the bands at 408 and 540 nm, which
Figure 3. UV-Vis spectra of the reaction mixture t-BuOK/DMSO to
evidences the formation of charger transfer (CT) complexes of
the presumed kind [NpPH2ꜙ t-BuO·]K+ (408 nm) or [Np2PHꜙ t-
which PH3 and BrNp were added stepwise and when necessary

6
Tetrahedron
ACCEPTED MANUSCRIPT
The data implies that phosphide-anion reacts with naphthyl
in vacuum and stored over molecular sieves (4 Å) under N2. Red
radical to give radical anion [NpPH2]ꜙ, which further undergoes
electron transfer to the next molecule of BrNp to form at the
beginning primary phosphine NpPH2 and then secondary- and
tertiary phosphines.
phosphorus (KSAN’ SIA, China), t-BuOK (Aldrich), t-BuONa
were all commercial samples which were used without further
purification. Liquid 1-bromonaphthalene (Alfa Aesar, 97%) was
freshly distilled before their utilization. All reaction glassware
and equipment were thoroughly cleaned and dried prior to use.
All experiments were carried out under Ar atmosphere, except
for work-up procedures.
Synthesis of di(1-naphthyl)phosphine oxide
Scheme 6. Probable CT complex formation
To a solution of t-BuOK (8.14 g, 72.5 mmol) in anhydrous
and degassed DMSO (73 mL), blown with argon and saturated
with dry phosphine, a solution of 1-bromonaphthalene (10.01 g,
48.3 mmol) in anhydrous DMSO (7 mL) was added dropwise at
70 °C for 1 h under stirring and continuous bubbling of the
phosphine. The reaction mixture was heated (70 °C) for 0.5 h in
the flow of phosphine, the phosphine feeding was stopped, but
3. Conclusion
In summary, the PCl3-free convenient phosphination of 1-
bromonaphthalene with PH3 in the superbasic system t-
BuOK/DMSO (70 oC) leading to di(1-naphthyl)phosphine and its
oxide has been developed. Reactivity of phosphide-anion toward
1-bromonaphthalene is demonstrated and it is found the reaction
proceeds through base-promoted radical nucleophilic substitution
(SRN1-type chemistry).
o
the mixture was continuously stirred for 1.5 h (70 C). In the 31P
NMR spectrum of the reaction mixture, the following signals
1
were observed: -62.03 (d, JPH 227 Hz) for 1-Np2PH, -33.37 (s)
1
for 1-Np3P and -2.49 (t, JPH 463 Hz) for 1-NpP(O)H2 in a ratio
of ~ 5:1.5:0.1. Trace amounts of 1,2-Np2PH (-49.78 ppm) and
1,1,2-Np3P (-22.70 ppm) were also formed. Then the mixture was
blown with argon, cooled and diluted with cold water (80 mL) to
give a white precipitate (1.15 g). The latter was filtered off,
washed with water (5×30 mL) and Et2O (3×25 mL), dried on the
air to get 1-Np3P (0.68 g). The filtrate was sequentially extracted
with Et2O (50 mL) and CH2Cl2 (2×50 mL).
4. Experimental section
4.1. General
The monitoring was carried out by 31P{1H} NMR
spectroscopy of the reaction mixtures. To correctly evaluate the
content of the reaction products basing on relative integral
intensity of signals in the 31Р NMR spectrum, we used pulse
sequence «zg30» (BRUKER standard pulse program) and
(a) Ether extract was washed with cold water (3×20 mL),
dried over K2CO3, the solvent was removed under reduced
pressure to give a white wax-like crude product (5.01 g), which
was heated under 1 Torr (100‒150 °C, sand bath) to sublimate
naphthalene (1.37 g) and to distill unreacted BrNp (0.95 g,
conversion 91%). The residue was dissolved in EtOH (22 mL),
white precipitate was filtered off, washed with EtOH (10×5 mL)
and dried in vacuo to give a creamy solid (0.62 g, 1-Np3P).
time of relaxation delay d1 = 5 s. The H, 13C and 31P NMR
1
spectra were recorded using a Bruker AV-400 spectrometer at
400.13, 100.62 and 161.98 MHz, respectively. The 1H NMR
chemical shifts are expressed with respect to residual protonated
CDCl3 (7.27 ppm), which served as an internal standard. The 13
C
NMR shifts are expressed with respect to the CDCl3 (77.0 ppm).
85% H3PO4/D2O was used as external standards for 31P NMR.
The FTIR spectra were recorded on a Bruker Vertex 70
spectrometer. The C, H microanalyses were performed on a Flash
EA 1112 SHNS-O/MAS analyzer, while the P contents were
determined by combustion method. Melting points were
established using a Kofler micro hot stage.
Secondary phosphine oxide 1-Np2P(O)H (2.30 g) was isolated
from alcoholic extract after removing the solvent and drying in
vacuum.
(b) CH2Cl2 extract was washed with brine (10% aq. sol. KCl),
orange precipitate was filtered off, dried over K2CO3 and the
solvent was removed to give white wax-like product (1.21 g).
The latter was heated under 1 Torr (100-150 °C, sand bath) to
sublimate naphthalene (0.17 g), the residue was washed with
EtOH (3×20 mL), the 1-Np3P (0.08 g) was filtered off, EtOH was
removed to afford 1-Np2P(O)H (0.65 g).
CW EPR spectra were recorded with FT X-band Brüker
ELEXSYS E 580 spectrometer (X-wave range 9.7 GHz).
Precision of the measurement of g-factor was ± 0.0002. CW
EPR-spectra were recorded at the following conditions:
amplitude modulation 0.5-1.0 G, receiver gain 60‒90 dB, time
constant 0.02 s, conversion time 0.04 s, microwave power 0.6325
mW. The monitoring of the reaction was carried out at 65‒85 °С
temperature in ampoules of 1.5 mm diameter directly in the
resonator of EPR spectrometer. The simulated spectra were
obtained using the WINEPR SimFonia 1.25 Program (Bruker
Inc. 1996). Concentration of PBN was 10-1-10-2 M/l. UV–Vis
Total yield of 1-Np2P(O)H is 2.95 g (45%). Total yield of 1-
Np3P is 1.38 g (23%). Yield of naphthalene is 1.54 g (27%).
Di(1-naphthyl)phosphine, Np2PH, the compound was
1
identified by H NMR, 31P NMR, and these data
were consistent with literature values.7
spectra were recorded on
a Perkin Elmer Lambda 35
1H NMR (CDCl3): 8.24 (m, 2H, H8), 7.92-7.79 (m,
o
spectrometer at 25-70 C). UV−Vis spectra of reaction mixture
(BrNp/t-BuOK (2.5×10−3 ÷ 5×10−4 mmol/L) measured in DMSO
using a 1 cm cuvette at rt under Ar atmosphere. FT-IR spectra
were recorded on a Bruker Vertex 70 spectrometer at ambient
temperature.
PH
6H, H3-5), 7.50 (d, 1H, JPH 227 Hz, PH), 7.48-7.44
8
1
9
2
7
(m, 4H, H6,7), 7.30 (dd, 2H, J 7.5 Hz, H2). 31P
NMR (CDCl3): -61.76 ppm (JPH 227 Hz). Found:
3
6
10
4
5
C, 83.41; H, 5.26. Anal. Calcd for C20H15P: C, 83.90; H, 5.28.
Di(1-naphthyl)phosphine oxide, 1-Np2P(O)H, white
Controlled generation of phosphine together with hydrogen
was rendered in a separate reactor by the addition of warm
aqueous solution of KOH (60%) to a suspension of red
o
powder, mp 168‒169 C. FTIR (neat), cm-1: 449, 664, 674, 757,
773, 944, 993, 1164, 1179, 1215, 1376, 1459, 1506, 1570, 1590,
1
o
phosphorus in toluene at 20‒50 C.30 Unused outlet PH3 was
1620, 2316, 2851, 2923, 2957, 3056. H NMR (CDCl3): 8.90 (d,
J 481 Hz, 1H, PH); 8.35 (m, 2H, H8), 8.05 (d, J 8.3 Hz, 2H, H4),
7.97 (d, J 7.2 Hz, 2H, H2), 7.92 (m, 4H, H3,5), 7.52 (m, 4H, H6,7).
absorbed by sol. 20% DMSO/aq.CuSO4 (or aq. Cu(OAc)2).
DMSO was dried over Al2O3 (2‒3 days) and distilled under KOH

7
13С NMR (CDCl3): 133.9 (d, J 11.5 Hz, C9), 133.5 (C7), 133.4 (d,
References and notes
ACCEPTED MANUSCRIPT
J 9.5 Hz, C10), 132.7 (d, J 11.5 Hz, C8), 129.1 (d, J 98.0 Hz C1),
129.1 (C4), 127.7 (C5), 126.7 (C6), 125.0 (d, J 14.5 Hz, C3), 124.9
(d, J 20.6 Hz, C2). 31P NMR (CDCl3): 18.85 (d, J 481 Hz, PH);
Found: C, 78.98; H, 4.93. Anal. Calcd for C20H15OP: C, 79.46; H,
5.00.
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Di(1-naphthyl)phosphinic acid, 1-Np2P(O)OH
Solution of di(1-naphthyl)phosphine oxide (0.1 g) in
chloroform (5 mL) was refluxed in air for 2 h. Then the solvent
was distilled under reduced pressure and residue was dried in
vacuum. Di(1-naphthyl)phosphinic acid was prepared in near
quantitative yield.
White powder, mp 198-201 oC, FTIR (KBr): 3055, 3008,
2955, 2922, 2854, 2632, 2289, 1955, 1646, 1619, 1591, 1568,
1505, 1456, 1432, 1382, 1334, 1212, 1178, 1152, 1025, 995, 951,
1
833, 800, 773, 753, 680, 566, 526, 479. H NMR (CDCl3): 9.58
(br, 1H, OH), 8.48 (d, J 8.5 Hz, 2H, H8), 8.16 (dd, J 16.3 and 7.2
Hz, 2H, H2), 7.92 (d, J 8.4 Hz, 2H, H4), 7.79 (d, J 8.1 Hz, 2H,
H5), 7.45-7.37 (m, 4H), 7.40-7.36 (m, 4H, H6,7), 7.29 (t, J 7.7 Hz,
2H, H3). 13С NMR (CDCl3): 133.5 (d, J 11 Hz, C9), 133.4 (d, J 11
Hz, C8), 133.3 (d, J 2 Hz, C7), 132.7 (d, J 11 Hz, C10), 128.9 (d, J
137 Hz, C1), 128.7 (C4), 127.1 (C5), 126.6 (d, J 5 Hz, C3), 126.1
(C6), 124.5 (d, J 15 Hz, C2). 31P NMR (CDCl3): 37.3 ppm. MS
m/z calcd for C20H15O2P: MS (M+ 315).
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4
3
1H, JHH 8.0 Hz, JPH 4.5 Hz, H8), 7.87 (d, 1H, J 7.5 Hz, H5),
7.82 (d, 1H, 3JHH 8.3 Hz, H4), 7.52 (dd, 1H, 3JHH 7.7 Hz, 3JHH 7.5
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3
3
2J 4.8 Hz, C2), 133.4 (C9), 132.8 (d, J 11.2 Hz, C10), 129.6 (C4),
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87.36; H, 5.13; P, 7.51. Found: C, 86.95; H, 5.05. MS m/z calcd
for C30H21P: M+ 427.
Acknowledgements
This work was supported by the President of the Russian
Federation (program for the support of leading scientific schools,
grant NSh-7145.2016.3) and the Russian Foundation for Basic
Research (Grant 15-03-01257). The authors are grateful to the
Baikal Analytical Center for the spectral measurements and RAS.
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