Mendeleev Commun., 2017, 27, 137–138
(100°C, 3 h), remains almost unchanged (for more details, see
produces resonance-stabilized carbanion B, in which the C–P
bond is attached to the phosphorus cluster. Subsequent cleavage
of the remaining P–P bonds within B by HO– anions eventually
gives the salt of (1,4-diphenylbut-3-en-1-yl)phosphinic (C) or/and
(1,4-diphenylbut-2-en-1-yl)phosphinic (C') acids. Finally, their
KH2PO2 reduction leads to the salt of acid 2, whose acidification
delivers free acid 2. The primary phosphine 3 is probably formed
either from phosphide anions [Pm]– in a similar way or through
superbase-catalyzed monoaddition of PH3 to diene 1. Phosphine
PH3 is a common by-product of reactions between red phosphorus
and alkali.
In summary, the one-pot transformation of 1,4-diphenylbuta-
1,3-diene to 1,4-diphenylbutylphosphinic acid, which represents
the first example of the straightforward phosphorylation of dienes
with the triad P/KOH/DMSO, has been implemented. The results
obtained extend the scope of the organophosphorus synthesis
based on the Trofimov–Gusarova reaction.2
Online Supplementary Materials). Thus, the formation of com-
pounds 4 and 5 as by-products of the reaction is likely due to the
side reduction of 1 with potassium hypophosphite, which is formed
in the reaction mixture. Importantly, the 13C NMR spectrum of
aqueous layer of the diluted reaction mixture contains signals of
the potassium salt of acid 2 and no peaks of the olefinic carbons
(Figure S2). This clearly indicates that this acid is originated
directly from the reaction of red phosphorus with 1, rather
than through H3PO2-assisted hydrogenation of possible initial
unsaturated species, e.g. (1,4-diphenylbut-3-en-1-yl)- or (1,4-di-
phenylbut-2-en-1-yl)phosphinic acids.
Basing on these results, we propose that the process is trig-
gered by the cleavage of P–P bonds of red phosphorus network
by hydroxide anions furnishing highly nucleophilic polynuclear
species, phosphide, [Pm]–, and phosphinite, [Pn–O]– (A), anions
(Scheme 2). Further addition of the phosphinite anion to diene 1
Authors are grateful to Baikal Analytical Center SB RAS for
the instrumental equipment.
P
P
P
P
P
P
HO–
2
P
O
P
P
Online Supplementary Materials
Supplementary data associated with this article can be found
in the online version at doi: 10.1016/j.mencom.2017.03.009.
P
–
,
– H2O
P
fragment of red
phosphorus
macromolecule
A
P
References
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Ph
Ph
–OH/H2O
P
P
O
1
P
Ph
Ph
B
Ph
P
Ph
O
O
O
Ph
Ph
or
P
O
H
H
C
C'
i, KH2PO2
ii, H+
Ph
3
1
O
Ph
P
2
4
OH
H
2
Scheme 2
‡
1,4-Diphenylbutylphosphinic acid 2. White crystals, mp 55–58°C
(hexane). 1H NMR (CDCl3) d: 10.25 (br.s, 1H, OH), 7.25–7.01 (m, 10H,
Ph), 6.97 (d, 1H, PH, 1JPH 543.8 Hz), 3.06 (td, 1H, C2H2, 2JHH 13.6 Hz,
3JHH 5.6 Hz), 2.78–2.62 (m, 3H, C2H2 and C4H2), 2.09–1.95 (m, 2H,
C1H and C3H2), 1.83–1.70 (m, 1H, C3H2). 13C NMR (CDCl3) d: 141.1
(i-C, PhC4), 138.4 (d, i-C, PhC1, 2JCP 12.6 Hz), 129.1 (o-C, PhC1), 128.6
(o-C, PhC4), 128.4 (m-C, PhC4 and PhC1), 126.0 (p-C, PhC4), 38.8 (d, C1,
1JCP 95.2 Hz), 33.4 (d, C2, JCP 7.3 Hz), 33.1 (C4), 27.8 (C3). 31P NMR
2
(CDCl3) d: 41.52 (dd, 1JPH 543.7 Hz, 2JPH 14 Hz). EI-MS, m/z: 274 [M]+.
FT-IR (KBr, n/cm–1): 2382 (m, nP–H), 1637 (br., nO–H), 1172 (s, nP=O), 967
(s, nP–O). Found (%): C, 69.91; H, 6.93; P, 11.04. Calc. for C16H19O2P
(%): C, 70.06; H, 6.98; P, 11.29.
Received: 1st September 2016; Com. 16/5036
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