Superbase-Assisted Selective Synthesis of Triarylphosphines from Aryl Halides and Red Phosphorus: Three Consecutive Different SNAr Reactions in One Pot

Article abstract of DOI:10.1002/ejoc.201901005

Aryl halides, ArX (Ar = Ph, 2-, 3- and 4-Tol, 1- and 2-Np, 4-C₆H₄CONH₂; X = F, Cl, Br), rapidly and exothermically (100–180 °C, 0.5–2 h) react with red phosphorus in superbase systems KOH/L, where L is a polar nonhydroxylic complexing solvent (ligand), such as NMP, DMSO, HMPA, to afford the corresponding triarylphosphines (Ar₃P) in up to 74 % yield (for X = F). Thus, three consecutive reactions of S_NAr (aromatic nucleophilic substitution) to form the three C(sp²)–P bonds are realized in one pot. The synthesis is mostly chemoselective (with rare exception): neither mono- nor diphosphines have been isolated. The best results were attained when aryl fluorides were treated with red phosphorus (P_n) in the KOH/NMP superbase system. This environmentally friendly, PCl₃-free synthesis of Ar₃P from available starting materials opens an easy and straightforward access to triarylphosphines, which are important ligands, synthetic auxiliaries, and components of high-tech- and medicinally oriented complexes.

Full text of DOI:10.1002/ejoc.201901005

DOI: 10.1002/ejoc.201901005
Communication
Red Phosphorus
Superbase-Assisted Selective Synthesis of Triarylphosphines
from Aryl Halides and Red Phosphorus: Three Consecutive
Different SNAr Reactions in One Pot
Svetlana F. Malysheva,[a] Vladimir A. Kuimov,[a] Natalia A. Belogorlova,[a]
Alexander I. Albanov,[a] Nina K. Gusarova,[a] and Boris A. Trofimov*[a]
Abstract: Aryl halides, ArX (Ar = Ph, 2-, 3- and 4-Tol, 1- and 2- ception): neither mono- nor diphosphines have been isolated.
Np, 4-C6H4CONH2; X = F, Cl, Br), rapidly and exothermically The best results were attained when aryl fluorides were treated
(100–180 °C, 0.5–2 h) react with red phosphorus in superbase with red phosphorus (Pn) in the KOH/NMP superbase system.
systems KOH/L, where L is a polar nonhydroxylic complexing This environmentally friendly, PCl3-free synthesis of Ar3P from
solvent (ligand), such as NMP, DMSO, HMPA, to afford the corre- available starting materials opens an easy and straightforward
sponding triarylphosphines (Ar3P) in up to 74 % yield (for X = F). access to triarylphosphines, which are important ligands, syn-
Thus, three consecutive reactions of SNAr (aromatic nucleophilic thetic auxiliaries, and components of high-tech- and medici-
substitution) to form the three C(sp2)–P bonds are realized in nally oriented complexes.
one pot. The synthesis is mostly chemoselective (with rare ex-
Introduction
was also employed for the synthesis of triphenylphosphine
using phenyl halides and sophisticated Ti complexes,
{Ti[NAr(tBu)]3, 3–5 equiv.}.[17]
Triarylphosphines, especially triphenylphosphine (Ph3P), are
most widespread organic phosphines, which represent a para-
mount interest for synthetic chemistry,[1] catalysis,[2] biomedici-
nes[3] and high-tech materials,[4] optoelectronics,[5] solar cells,[6]
organometallopolymers,[7] etc.
However, until now red phosphorus (Pn) remained almost
ignored as a starting platform for the synthesis of triarylphos-
phines. In 1984 Bornancini prepared triphenylphosphine (80 %
yield) from PhI in the system Pn/Na/tBuOH/NH3(liq.) under UV
irradiation (350 nm),[18] but further this finding was not devel-
oped. It was reported that the heating (230 °C, 16 h) of PhI with
red phosphorus in the presence of NiBr2 and iron filings led to
triphenylphosphine (the yield was not given).[19] Functionalized
fluorobenzenes possessing strong EWG (electron-withdrawing
groups) reacted with red phosphorus in the system Li/tBuOH/
NH3(liq.) to give the corresponding functionalized Ar3P in 37–
60 %.[20]
Industrial synthesis of triphenylphosphine includes interac-
tion of PCl3 with melted sodium and phenyl halides at 200 °C.[8]
[9]
Another route to triphenylphosphine is the reaction of PCl3
or (PhO)3P[10] with phenylmagnesium halides in Et2O or
THF.[11]Also known is a method based on reaction of PCl3 with
lithiated benzenes (phenyl halides + nBuLi).[12] The reaction of
PCl3 with AlCl3 (or Al powder) and PhCl at 180–200 °C was
claimed to give to triphenylphosphine in 91 %.[13]
Now, all these PCl3 based syntheses of triphenylphosphine
are perceived as environmentally unfriendly,[14] which are
strongly desirable to be substituted by greener approaches,
particularly, using elemental phosphorus. Sinyashin et al. had
shown that triphenylphosphine can be synthesized electro-
chemically in 20–60 % yield from white phosphorus (P4) and
PhBr or PhI at 25–50 °C in the presence of Ni complexes apply-
ing soluble metallic (Zn, Al, Mg) anodes and DMF or MeCN as
solvents.[15] According to Mezailles et al.,[16] triphenylphosphine
was synthesized in good yield from P4, nanosized potassium
metal/graphite composite and PhI in PhMe. White phosphorus
In the last decades, we were systematically developing the
synthesis of organophosphorus compounds (phosphines, phos-
phine oxides, phosphinic and phosphonic acids) using red
phosphorus and various electrophiles in the multiphase super-
base systems of the type KOH/H2O/DMSO (or HMPA) or under
phase-transfer conditions (KOH/H2O/organic solvent/phase-
transfer catalyst).[21] Among electrophiles, acetylenes,[21] alk-
enes,[22] different organic halides,[21a,21c,23] heterocyclic halides
(2-halopyridines)[24] and some condensed aromatic halides
were employed.[21c] However, phenyl halides[23a] turned out to
be entirely inert towards polyphosphide anions generated from
red phosphorus in the superbase systems under conditions
suitable for the synthesis of aforementioned organophosphorus
compounds.
[a] A. E. Favorsky Institute of Chemistry, Siberian Branch of the Russian
Academy of Sciences,
Favorsky st., 1, Irkutsk 664033, Russia
E-mail: boris_trofimov@irioch.irk.ru
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under https://doi.org/10.1002/ejoc.201901005.
We report that the longstanding problem, namely the syn-
thesis of triarylphosphines using red phosphorus and aryl hal-
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Table 1. Optimization of the reaction conditions.[a]
[a] Reaction conditions: molar ratio of ArX (75 mmol)/Pn/KOH·0.5H2O as 1:1.3:5.13; L (40 mL), argon (Tol = tolyl, Np = naphthyl, Bza = benzamide, DMF =
dimethylformamide, NMP = N-methyl-2-pyrrolidone, DMSO = dimethyl sulfoxide, HMPA = hexamethylphosphorus triamide). [b] In brackets exothermic peaks
are given. [c] Yield of isolated product. (in brackets yield basing on reacted ArX). [d] Also, Ph2PMe (10 %) and PhSMe (≈ 1 %) were isolated. [e] Also, Ph2PMe
(≈ 9 %) and PhSMe (≈ 1 %) were isolated. [f] Molar ratio of ArX (75 mmol)/Pn/KOH·0.5H2O as 1:1:3.85. [g] Fix temperature. [h] Molar ratio of ArX (75 mmol)/
Pn/KOH·0.5H2O as 1:1.5:3.85. [i] Also, Ph2PMe (≈ 3 %) and Ph2PEt (≈ 2 %) were isolated. [j] Also, Ph2PSMe (5.3 %), Ph2PMe (≈ 1 %) were formed. [k] Molar ratio
of ArX/Pn/KOH·0.5H2O as 1: 2.8: 8.7. [l] Also 2-Tol2PH was formed in ≈ 1:1 molar ratio (isolated as phosphine oxide in 15 % yield).
ides has now been solved, and the synthetic details are pre- (2–5 min, 120–180 °C, depending on the L nature), the tempera-
sented in this communication. This goal was achieved due to ture of the reaction mixture drops to 100 °C during 0.5–1 h, and
the following two essential amendments to the previous meth- triarylphosphines thus obtained are isolated by conventional
odology: i) the basicity enhancement of the multiphase super-
base systems (which disassemble Pn 3D molecules to super-
nucleophilic polyphosphide anions) by exclusion of water from
their composition, and ii) the rapid heating of the reaction mix-
ture (up to 100–115 °C) to initiate short exothermic process
thereby allowing completion of the synthesis within 0.5–1 h.
Representative data concerning the influence of the reaction
conditions and structure of the ArX on the yield of triarylphos-
phines are shown in Table 1.
workup (see the Supporting Information for details). If the exo-
thermic effect is quenched by outer cooling, the yield of triaryl-
phosphines is remarkably decreased (sometimes, twice as less).
Some amounts of the PH3 mixture[14] formed in the process are
oxidized by the H2O/DMSO/CuSO4 solution (see the Supporting
Information), or can be used as synthetic reagent, e.g. for prepa-
ration of organic phosphines.[25]
The overall redox process is accompanied by formation of
oxidized phosphorus molecules, mostly potassium phosphite
(31P NMR monitoring), which, if necessary, can be isolated as a
product.
Results and Discussion
As seen from Table 1, the major factors which influence the
triarylphosphines yield are the nature of polar complexing sol-
The syntheses were implemented by immersing the reaction
mixture (Pn, ArX, KOH/L) into the preliminarily heated (115 °C) vent (L) as a ligand of a superbase system (KOH/L) and the
glycerol bath upon stirring. After the short exothermic effect structure of aryl halides, mainly the nature of halogen. The best
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yields of triphenyl- (2a), tritolyl- (2b, 2c), and trinaphthylphos- phines using chloroarenes have not been successful enough
phines (2f, 2g), which span 51–74 % were attained when the (Table 1, entries 6–12, 19, 22 and 29).
reaction was conducted in the KOH/NMP superbase system
with corresponding aryl fluorides (entries 2, 17, 20, 26, 30). The
close results for the same aryl fluorides were obtained when
the reaction was implemented in the KOH/HMPA superbase sys-
tem, the yield ranging 54–70 % (entries 5, 18, 21, 27, 31). In
view of adverse physiological properties of HMPA as a sol-
vent,[26] the KOH/NMP should be considered as a system of
choice. It is worthwhile to note that in the KOH/HMPA system
the most significant exothermic effect (132–180 °C) have been
observed. That could have a negative effect on scaling up this
protocol. Surprisingly, the KOH/DMSO system which previously
most often was used for the Pn-based syntheses of phosphines
and phosphine oxides,[21] in this case proved to be inferior: the
yield of Ph3P from PhF was 41 % only, i.e. by 33 % lower than
in KOH/NMP system (entry 2 vs. 3). Besides, this reaction was
complicated by the side-methylation of the intermediate di-
phenylpolyphosphide species (entry 3), resulting in formation
of Ph2PMe (yield ≈ 10 %). In the experiments with PhCl and
PhBr the same methylation was observed, the yield of Ph2PMe
being 9 % and 1 % respectively (entries 7, 14). In some experi-
ments, methyl phenyl sulfide, MeSPh, was also detectable in
≈ 1 % yield (entries 3, 7–9), that (together with above methyl-
ation) indicates an insignificant reductive destruction of DMSO.
This is also confirmed by the detection of Ph2PSMe (yield ≈
5 %) in the synthesis of Ph3P from PhBr (entry 14).
Next, the effect of aromatic moiety of aryl fluorides on the
yield of Ar3P has been examined. The aryl fluorides were chosen
because PhF provided the best yields of triphenylphosphine.
As follows from Table 1, methyl substituents in the benzene
ring decrease the yields of tri(tolyl)phosphines, which with
3- and 4-tolyl fluorides (in the KOH/NMP system) are 59 % and
51 % (entries 17, 20). In the case of 2-tolyl fluoride the corre-
sponding tri(2-tolyl)phosphine was isolated just in 19 % yield
(entry 23) along with di(2-tolyl)phosphine (yield 15 %). The lat-
ter result is the only example of the secondary phosphine syn-
thesis in this reaction, which is usually resulted in formation of
exclusively tertiary phosphines. The observed depression of the
triarylphosphines yield compared to Ph3P is the expected out-
come of negative influence of the electron-donating methyl
substituent on the aromatic nucleophilic substitution that is ad-
ditionally aggravated by the steric shielding for 2-tolyl fluoride.
A similar regularity takes place also for the KOH/HMPA system
wherein 2-tolyl fluoride gave no tritolylphosphine 2d at all (en-
try 24).
In accordance with the assumed reaction mechanism as aro-
matic nucleophilic substitution were the negative results for
such π-electron-donating substituents as amino-(3-, 4-), meth-
oxy-(3-, 4-), 4-chloro-, and 3-bromo- in the benzene ring: only
traces of secondary phosphines were detected (31P NMR) in the
reaction mixture for these fluoroaromatics.
Under the same conditions, in sulfolane, the process pro-
ceeded without an exothermic effect (100–120 °C) resulting
only in 34 % yield of Ph3P though free of any contaminants
(entry 4). This experiment shows again that a rapid preheating
is indeed necessary to get a good yield of Ph3P. Note that DMF
appeared to be absolutely insufficient ligand of KOH to pro-
mote the synthesis of triphenylphosphine: only traces of pri-
mary phenyl- and secondary diphenylphosphines were de-
tected in the reaction mixture (entry 1). Obviously, the deep
alkaline solvolysis of DMF as aliphatic amide occurs in this case.
The key role in activation of red phosphorus in this redox reac-
A modest yield of the tertiary phosphine, obtained from 4-
fluorobenzamide, despite the electron-withdrawing substituent
(H2NCO) in the benzene ring (30 %), is likely caused by a partial
decomposition of the amide function under the action of active
hydroxide and polyphosphide anions to give the corresponding
benzoic acid derivative (entry 25).[28]
Surprisingly good yields of corresponding tertiary phos-
phines 2f, 2g have been obtained from 1- and 2-fluoronaphth-
alenes (67 and 60 % in KOH/NMP or 70 and 54 % in KOH/HMPA
system), despite their obvious steric encumbrance, so in these
cases the loadings of Pn and KOH were necessary to be in-
tion and polyphosphide anions generated from Pn belongs to creased about twice as much (entries 27 vs. 28). Notably that 1-
a metal cation of the superbase media that follows from the fluoronaphthalene wherein the fluoride atom is more sterically
drastic reduction of the triphenylphosphine yield from 69 shielded than in its 2-isomer provides a higher yield of the tar-
get phosphine 2f.
to 6 % when the KOH/HMPA system was replaced by NaOH-
tailored its analog.
It should be underlined that most of the syntheses were per-
formed on the gram (up to 5 g) scale thereby demonstrating
good prospects for a larger scale application of the developed
methods.
A very strong influence on the yield of triphenylphosphine
exerts the nature of halogen atom in the benzene ring. Under
the best conditions (KOH/NMP), the highest yield was reached
in the case of fluorobenzene (74 %), while for chloro-, bromo-
and iodo-analogs the yield of Ph3P dramatically drops: 36, 9
and 0 %, correspondingly (entries 6, 13, 16). This fact is in good
agreement with a general regularity of the aromatic nucleo-
philic displacement (SNAr) that the fluorine atom in an aromatic
ring undergoes nucleophilic aromatic substitution much faster
than other halogens.[27]
Overall, the best practically result of this investigation is the
efficient (74 % yield) straightforward synthesis of triphenylphos-
phine (most widely used organic phosphine), from red phos-
phorus and fluorobenzene in the KOH/NMP superbase system.
Despite that fluorobenzene is 1.5–2.5 times more expensive
than chlorobenzene (depending on purity and supplier), the
yield of triphenylphosphine (in NMP) from the former is three
times higher than from chlorobenzene (74 % and 24 %, respec-
tively). Although, in HMPA, the best yield of Ph3P from chloro-
benzene reached 43 % (Table 1, entry 10), the practical applica-
tion of this solvent has no future due to its toxicity (carcinogen-
From the practical point, the most attractive substrates are
chloroarenes as available and inexpensive, however our at-
tempts to improve the yields of corresponding triarylphos-
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icity) and much higher cost compare to NMP. On the contrary, submicro- and nanosized particles with a higher surface energy
the latter is a readily available, industrially produced, biologi- may also contribute to the easiness of the nucleophilic displace-
cally friendly, non-toxic solvent,[29] applied as a penetration en- ment under question. In the superbase media with their lower
hancer for topically administrated drugs, and as a vehicle for proton activity, the above supernucleophiles are poorly solv-
cosmetics.
An intriguing feature of the reaction studied is the selective
formation of triarylphosphines: neither corresponding primary
no secondary phosphines are usually detectable in the reaction
mixtures. Formally the synthesis proceeds as consecutive nu-
ated and therefore should have even a higher reactivity. All
these should facilitate the nucleophilic displacement of halogen
atoms in aromatic rings by the polyphosphide P-centered an-
ions.
In fact, the real nucleophiles are oligophosphide and aryl-
cleophilic displacement of halogen in the aromatic moiety by terminated oligophosphide anions. The preferred further forma-
the anions P3–, ArP2–, Ar2P–, resulted from disassembling of the tion of phosphides bearing two or three aryl groups is likely
Pn 3D-network under the action of active OH-anion.
due to the higher nucleophilicity of P atom adjacent to the
organic moiety, compared to the P-centered anion bound with
two other P atoms. Indeed, the cleavage of the P–P bond by
hydroxide anion in the intermediate aryl-oligophosphides F
(Scheme 2), should be preferably occur, so that the negative
charge, thus formed, could be distributed over the arene moi-
ety (a benzylic type anion). The alternative cleavage of the same
P–P bond seems to be less preferred because anionic center in
this case (G) is affected by the repulsive interaction with the
electron lone pairs (ELP) of the two neighboring phosphorus
atoms. Consequently the next molecules of aryl halides will
preferable interact with intermediate C to locate another aryl
substituent at the same P atom. The final formation of triaryl-
phosphines should be even more favorable since it will involve
the P-centered anion stabilized by 2 neighboring aryl substitu-
ents. Correspondingly the consecutive attacks of hydroxide an-
ion should be directed at the P-atoms which already bear
hydroxide substituents owing to the progressively increasing
positive charge on the P atom. The approximated rationaliza-
tion, here presented, helps to understand the high selectivity
of the reaction i.e. the predominant formation of triarylphos-
phines and potassium phosphite and hypophosphite.
Such poorly solvated hydroxide anions in the frustrated ion
pairs K+OH–, wherein the potassium cations are specifically co-
ordinated with the complexing strongly polar solvent (L), repre-
sent the most reactive species in the superbasic media used in
this case. In view of the known low activity of arylhalides in the
reaction SNAr (usually activation by strongly EWG-substitution
or metal-catalysis is required), the observed rapid and exhaus-
tive synthesis of Ar3P via the three different in nature phos-
phorus-centered nucleophiles should be rated as abnormal
phenomenon. Obviously, this is caused by the mechanistic
specificity of the process under investigation which progresses
in multiphase superbasic media.
Apparently, the process starts with P–P bond cleavage by
hydroxide anion to form polyphosphides A, as a part of Pn net-
work, and the oxidized counterpart of the cleaved Pn network
terminated by HP=O-groups (Scheme 1). The polyphosphide
anion species, undergoing in time the further disassembling,
react with aryl halides to form aryl polyphosphide intermedi-
ates B (the first SNAr act). The consequent cleavage of the P–P
bond adjacent to the P–Ar moiety by the OH-anion leads to the
P-centered intermediate anions C. This polymeric anions C, after
the reaction with the next molecule of ArX, gives the diarylpoly-
phosphide intermediates D (the second SNAr act), which still
remains in the polyphosphide aggregates, probably nanosized
and, hence, cannot be released into the solution. Finally, the
hydroxide-assisted cleavage of the P–P bond neighboring PAr2
terminal group followed by the arylation of the diarylphosphide
anion E thus formed (the third SNAr act) affords triarylphos-
phine 2 (Scheme 1).
The polyphosphide P-centered anions A, C should have an
enhanced nucleophilicity, i.e. they should be supernucleophiles,
due to the α-effect of adjacent phosphorus atoms that is ex-
pressed in a lower ionization potential and higher polarizability.
The possible existence of the polyphosphides species as micro-,
Scheme 2. Two ways of polyphosphide intermediate formation.
Scheme 1. Plausible mechanism for the formation of Ar3P.
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The short thermal jump in the beginning of the process (the
temperature/time curves, see the Supporting Information) can
be roughly estimated in terms of the bond breaking/bond
forming during the disassembling of the Pn 3D network under
the action of the hydroxide anions (Pn → A, B → C, D → E,
Scheme 1). Indeed, according to,[30] the energy of P–P bonds,
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P=O and P–H bonds are ≈ 640 and ≈ 300 kJ/mol that corre-
sponds to the approximated energy balance as ≈ +700 kJ/mol,
i.e. the process is to be actually exothermic.
[6]
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Conclusion
Triarylphosphines, top requested ligands, synthetic intermedi-
ates and components of high-tech and bioactive metal com-
plexes, have become much more easily accessible owing to
their selective synthesis from red phosphorus (Pn) and aryl
fluorides in the superbasic media KOH/polar non-hydroxylic
complexing solvent-ligand (L) developed here. The process is
realized via three consecutive different SNAr reactions involving
polyphosphide supernucleophilic species generated from the
disassembling of the Pn molecule under the action of hydroxide
anion. The synthesis is readily scalable and avoids toxic, irrita-
tive and ecologically malignant phosphorus chlorides, organo-
metallics, and harsh conditions inherent in previous methods.
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Acknowledgments
The research has been carried out in accordance with the ap-
proved plans for research projects at the IPC RAS State Registra-
tion No. AAAA-A16-116112510005-7. We thank the Baikal
Analytical Centre for collective use of the Siberian Branch of the
Russian Academy of Sciences for the equipment.
[15]
Keywords: Red phosphorus · Phosphines · Aromatic
substitution · Synthetic methods · Superbase systems
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