The reaction activity of aromatic carbonyl compounds with diphenylphosphine oxide studied by 31P NMR

Article abstract of DOI:10.1080/10426507.2012.717137

A series of α-hydroxyphosphine oxides were prepared by the reactions of diphenylphosphine oxide and aromatic carbonyl compounds and characterized by ¹H NMR, ¹³C NMR, ³¹P NMR, FT-IR, ESI-MS, and HR-MS spectra. The reaction rates and experimental conditions of aromatic aldehydes and aromatic ketones were obviously different due to the activity of their carbonyls. The different substituents of the aromatic aldehydes affected the reaction rate too, and the quantitative reactivity of their substituent conformed to the Hammett equation. The results were confirmed by ³¹P NMR spectroscopy.

Full text of DOI:10.1080/10426507.2012.717137

This article was downloaded by: [Universitat Politècnica de València]
On: 28 October 2014, At: 20:27
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Phosphorus, Sulfur, and Silicon and the
Related Elements
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/gpss20
The Reaction Activity of Aromatic
Carbonyl Compounds with
Diphenylphosphine Oxide Studied by 31P
NMR
Jinyun Zheng a , Xiangming Feng a , Yujian Yu a , Xiaomin Zhen a &
Yufen Zhao a b
a Key Laboratory of Chemical Biology and Organic Chemistry of
Henan Province, College of Chemistry and Molecular Engineering ,
Zhengzhou University , Zhengzhou , China
b Department of Chemistry and Key Laboratory for Chemical Biology
of Fujian Province , Xiamen University , Xiamen , China
Accepted author version posted online: 09 Aug 2012.Published
online: 22 Jul 2013.
To cite this article: Jinyun Zheng , Xiangming Feng , Yujian Yu , Xiaomin Zhen & Yufen Zhao (2013)
The Reaction Activity of Aromatic Carbonyl Compounds with Diphenylphosphine Oxide Studied
by 31P NMR, Phosphorus, Sulfur, and Silicon and the Related Elements, 188:8, 1080-1087, DOI:
10.1080/10426507.2012.717137
To link to this article: http://dx.doi.org/10.1080/10426507.2012.717137
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the
“Content”) contained in the publications on our platform. However, Taylor & Francis,
our agents, and our licensors make no representations or warranties whatsoever as to
the accuracy, completeness, or suitability for any purpose of the Content. Any opinions
and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content
should not be relied upon and should be independently verified with primary sources
of information. Taylor and Francis shall not be liable for any losses, actions, claims,
proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or
howsoever caused arising directly or indirectly in connection with, in relation to or arising
out of the use of the Content.

This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &
Conditions of access and use can be found at http://www.tandfonline.com/page/terms-
and-conditions

Phosphorus, Sulfur, and Silicon, 188:1080–1087, 2013
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2012.717137
THE REACTION ACTIVITY OF AROMATIC CARBONYL
COMPOUNDS WITH DIPHENYLPHOSPHINE OXIDE
STUDIED BY 31P NMR
Jinyun Zheng,1 Xiangming Feng,1 Yujian Yu,1 Xiaomin Zhen,1
and Yufen Zhao1,2
1Key Laboratory of Chemical Biology and Organic Chemistry of Henan Province,
College of Chemistry and Molecular Engineering, Zhengzhou University,
Zhengzhou, China
2Department of Chemistry and Key Laboratory for Chemical Biology of Fujian
Province, Xiamen University, Xiamen, China
GRAPHICAL ABSTRACT
Abstract A series of α-hydroxyphosphine oxides were prepared by the reactions of
1
diphenylphosphine oxide and aromatic carbonyl compounds and characterized by H NMR,
13C NMR, 31P NMR, FT-IR, ESI-MS, and HR-MS spectra. The reaction rates and experimental
conditions of aromatic aldehydes and aromatic ketones were obviously different due to the
activity of their carbonyls. The different substituents of the aromatic aldehydes affected the
reaction rate too, and the quantitative reactivity of their substituent conformed to the Hammett
equation. The results were confirmed by 31P NMR spectroscopy.
Keywords Diphenylphosphine oxide; aromatic aldehyde; Hammett’s plot; 31P NMR tracking
INTRODUCTION
Diphenylphosphine oxide containing a P–H bond is a useful synthetic intermediate. It
undergoes addition reaction with terminal alkynes and some carbonyl compounds readily.
In the functional material fields, diphenylphosphine oxide plays an important role. Polymers
with phosphine oxide moieties have major advantages, such as good flame-retardant prop-
erties,1 high thermal oxidative stability, enhanced solubility in organic solvents, improved
miscibility, and good adhesion to other compounds. Light-emitting molecules, such as car-
bazole, fluorene, dibenzofuran, and 4-4ꢁ-biphenyl,2–5 containing the diphenylphosphoryl
Received 23 May 2012; accepted 27 July 2012.
The authors would like to thank the National Natural Science Foundation Committee of China for financial
support to this work (No. 20732004).
Address correspondence to Jinyun Zheng, Key Laboratory of Chemical Biology and Organic Chemistry of
Henan Province, College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450052,
China. E-mail: zhengjy@zzu.edu.cn
1080

REACTION ACTIVITY OF AROMATIC CARBONYL COMPOUNDS
1081
Figure 1 Synthesis of diphenylphosphine oxide and aromatic carbonyl compounds.
moieties showed that the polar phosphoryl group (P O) can improve electron injection
properties, impart high oxidative and thermal stabilities, and lower the operating voltage.
In the nucleophilic addition reaction of carbonyl compounds, the qualitative and quan-
titative studies of activity of the organic phosphorus nucleophilic reagents and the effects
of substituent of aromatic carbonyl compounds are important and interesting. Although the
reaction of diphenylphosphine oxide and benzaldehyde was reported in the 1950s, and later
several single crystal structures of (diphenylphosphoryl)phenyl methanol were obtained,6–8
the reaction conditions and the details of effects of the substituent were not researched,
especially the ring of benzaldehyde with electron-donating group. In this paper, we report
a different synthetic method of diphenylphosphine oxide with various aromatic aldehydes
including hexakis(4-formylphenoxy) cyclotriphosphazene, and ketones (Figure 1). A series
of (diphenylphosphinyl)phenyl ethanols were obtained, which can be used as the ligand for
the rhodium-catalyzed hydroformylation of aryl alkenes.9 The different reaction conditions
of aromatic aldehydes and ketone were discussed, and the effect of different substituents
of the benzaldehydes was also studied in detail, and confirmed by 31P NMR tracking.
RESULTS AND DISCUSSION
Table 1 shows the results of the diphenylphosphine oxide reacting with different
aromatic carbonyl compounds. The reaction time exhibited obvious difference due to
Table 1 The reaction results of diphenylphosphine oxide with aromatic carbonyl compounds
Product
Reactive condition
Reaction time
mp/◦C
Yield (%)
31P NMR δ/ppm
3a
3b
3c
3d
3e
3f
3g
3h
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
50 min
7 min
30 min
100 min
50 min
4 h
2 h
12 h
4 h
24 h
152–153
190–191
182–183
156–157
148–149
160–161
115–116
132–137
166–168
191–192
85
69
76
90
91
82
62
65
76
93
28.2
28.6
28.1
28.0
27.5
28.1
36.6
30.6
9.2, 31.0
23.4
Reflux, nitrogen
3i
r.t.
r.t.
Ph2P(O)OH

1082
J. ZHENG ET AL.
benzaldehyde (50 min) and acetophenone (>12 h), and the experimental conditions of
acetophenone (reflux, nitrogen protecting) were more rigorous than benzaldehydes (r.t.,
air). The results show that the diphenylphosphine oxide reacted readily with different
aromatic aldehydes, but difficultly with aromatic ketone. Due to steric and electronic factors,
aromatic aldehydes are more reactive in nucleophilic addition than acetophenone. With one
group being the small hydrogen atom, the central carbon of the tetrahedral product formed
from an aldehyde is less crowded and the product is more stable. With acetophenone, the
phenyl and methyl at the carbonyl carbon cause greater steric crowding in the tetrahedral
product and make it less stable. We also studied the reaction of aliphatic ketone, such as
acetone. The experimental conditions were more rigorous than benzaldehydes, but milder
than acetophenone. Without the protection of nitrogen, the solution refluxing for 7 h, the
product was obtained as white crystals.
Table 1 shows the reactive condition of acetophenone is under nitrogen, which is dif-
ferent from benzaldehydes. Because when diphenylphospnine oxide reacted with acetophe-
none in the presence of air, it underwent oxidation reaction and obtained diphenylphosphinic
acid. We next investigated the influence of oxygen on the reaction of acetophenone. When
the oxygen was strictly removed from the reaction system, the product of diphenylphos-
phinic acid was dramatically suppressed, and even disappeared. In other words, the oxida-
tion and addition reactions compete with each other. If the carbonyl is active, the addition
reaction is dominant; on the contrary, if the carbonyl is not active, the oxidation reaction is
dominant.
As for the aromatic aldehyde series, the reaction time also exhibited obvious dif-
ference due to the different substituents of the benzaldehydes. The reaction time of
p-nitrobenzaldehyde was only 7 min, the p-bromobenzaldehyde was 30 min, the ben-
zaldehyde was 50 min, the hexakis(4-formylphenoxy) cyclotriphosphazene was 4 h, the
p-methoxybenzaldehyde was 100 min, and the p-hydroxybenzaldehyde was 4 h. In brief,
the benzaldehydes containing the electron-withdrawing groups increased the rate of the
reaction, while the electron-donating group slowed down the reaction because the electron-
withdrawing substituent caused the carbonyl carbon to be more positive and the addition
reaction to be more favorable. What deserves our attention is that the reaction times of the
ortho-substituent benzaldehydes were shorter than the para-substituent benzaldehyde due
to the ortho-effect.
The effects of substitution on the properties of benzaldehydes have not been sys-
tematically investigated. Hammett noticed that the effects of meta and para substitution
on the acidity constant of benzoic acids followed a linear relationship. Later, the Hammett
Equation has been applied to a variety of substituent effects on a wide range of molecular
systems.10,11 The Hammett Equation is log(k/k0) = ρσ, where K is the rate constant for
a substituted benzene derivative, and K0 is the rate constant for the reaction with benzene
derivatives. The slope of the line is ρ; for the benzoic acid series, ρ = 1, but it varies for
other systems. If ρ > 1, the system is more sensitive to substitution than the reference
benzoic acid system, while if ρ < 1, the system is less sensitive to substitution. The sign of
σ is the substituent constant, which provides a measure of the degree to which a substituent
releases electron density to a benzene ring. This electron release or withdrawal includes
effects due to both electronegativity and resonance. Different parameters11 have been deter-
mined depending on whether the substituent is para to the functional group, or meta to it.
Ortho values generally do not follow a linear relationship, because steric hindrance effects
are present in addition to the electronic ones. In this paper, the quantitative correlation
between the substituents of aromatic aldehydes and compound reactivity was studied by
the Hammett equation. Figure 2 displays the Hammett’s plot of para- and meta-substituted

REACTION ACTIVITY OF AROMATIC CARBONYL COMPOUNDS
1083
1.2
0.8
0.4
0.0
-0.4
-0.8
-0.4
0.0
0.4
0.8
1.2
σ
Figure 2 The Hammett’s plot of substituted benzaldehydes (ρ = 1.196).
benzaldehydes, which exhibited the linear relationship of the different benzaldehydes. For
this system, since ρ = 1.196, and ρ > 1, hence this system is more sensitive to substituent
than the reference benzoic acid system.
The reactions of diphenylphosphine oxide and aromatic aldehydes were monitored
by 31P NMR spectra. Take products 3b, 3c, and 3d as the representative example. The
reactions were carried out in the nuclear magnetic tube without adding Et3N. Figure 3
shows the reaction of p-nitrobenzaldehyde and diphenylphosphine oxide monitored by 31P
NMR spectra. When p-nitrobenzaldehyde was added to the reactive system, the signal at δ
Figure 3 The reaction of p-nitrobenzaldehyde and diphenylphosphineoxide monitored by 31P NMR spectra.

1084
J. ZHENG ET AL.
Figure 4 The reaction of p-bromobenzaldehyde and diphenylphosphine oxide monitored by 31P NMR spectra.
Figure 5 The reaction of p-methoxybenzaldehyde and diphenylphosphine oxide monitored by 31P NMR spectra.

REACTION ACTIVITY OF AROMATIC CARBONYL COMPOUNDS
1085
28.6 attributed to the product appeared immediately as a strong peak, and the signal at δ
18.2 attributed to the diphenylphosphine oxide was relatively weak. With the progress of the
reaction, the peakof diphenylphosphineoxidebecameweaker and weaker until disappeared.
In brief, the reaction took place rapidly with the total reaction time of 7 min. Figure 4 shows
the reaction of p-bromobenzaldehyde and diphenylphosphine oxide monitored by 31P NMR
spectra. When the reaction began, the signal at δ 28.1 attributed to the product appeared
immediately as a weak peak, and the signal of diphenylphosphine oxide was relatively
strong. With the progress of the reaction, the peak of product became stronger and stronger,
and the peak of diphenylphosphine oxide became weaker and weaker until it disappeared.
The reaction took place mildly within a reaction time of 30 min. Figure 5 shows the reaction
of p-methoxybenzaldehyde and diphenylphosphine oxide monitored by 31P NMR spectra.
When the reaction began, the product did not appear at once. With the progress of the
reaction, the signal at δ 26.7 attributed to the product appeared, and the reaction took place
slowly in a total reaction time of 100 min. In brief, the experimental data including reaction
time and reaction rate were consistent with the 31P NMR trace.
CONCLUSIONS
In conclusion, the reaction of diphenylphosphine oxide with aromatic carbonyl com-
pounds was studied in detail, including the effects of substitution. The experimental condi-
tions of acetophenone were more rigorous than aromatic aldehydes, and the reaction rate was
slower than aromatic aldehydes. The aromatic aldehyde containing electron-withdrawing
group increased the rate of the reaction, and the one containing electron-donating group
slowed down the reaction. The quantitative correlation between the substituents of aromatic
aldehydes and compound reactivity conformed to the Hammett equation. The reaction re-
sults were confirmed by 31P NMR trace experiments.
EXPERIMENTAL
Instruments and Reagents
The NMR (400 MHz) spectra were obtained using a Bruker AM 400 spectrometer
with deuterated DMSO and CDCl3 as solvents. Chemical shifts (δ values) are given in
ppm with tetramethylsilane as an internal standard. The 31P NMR (162 MHz) spectra were
1
referenced relative to 85% H3PO4 (δ = 0 ppm) with broadband H decoupling model.
ESI-MS and HR-MS were recorded on Bruker Esquire 3000 electrospray ion trap mass
spectrometer and Water Q-Tof Micro mass spectrometer, respectively. Infrared spectra were
recorded on a Shimadazuir-408 spectrometer in the range of 4000–400 cm−1, and samples
were prepared as KBr pellets. The m.p.s were obtained using a micro m.p. determination
instrument XT4A (Beijing Keyi Electro-optic Instrument Plant, Beijing, China).
Diphenylphosphine oxide was prepared by the hydrolysis reaction of
chlorodiphenylphosphine12 (yield 95%), m.p. 54–55 oC. 1H NMR (CDCl3) δ/ppm:
7.98–8.02 (m, 10H), 8.11 (d, JP-H = 468 Hz, 1H), 31P NMR (CDCl3) δ/ppm: 18.1. The
other reagents were used as supplied.
The 31P NMR tracking experiments: In an NMR tube, were placed THF (0.5 mL),
diphenylphosphine oxide (0.01 mmol), and different aryl aldehyde (0.01 mmol) in sequence,
followed by recording of the spectra.

1086
J. ZHENG ET AL.
Synthesis of Compounds 3a–g and 3i
Compounds 3a–g and 3i were prepared by the nucleophilic addition of diphenylphos-
phine oxide and aromatic aldehyde in a similar process. The synthesis of product 3d is given
as an example: Into a 50 mL round bottom flask equipped with an electronmagnetic stirrer,
THF (20 mL), diphenylphosphine oxide (1.01 g, 5 mmol) and p-methoxybenzaldehyde
(0.6 mL, 5 mmol) were placed in sequence. The solution was stirred at r.t. Then, two
drops of Et3N were added to the solution. Immediately, a solid appeared, and the solution
changed from clear to thick. The mixture was monitored by thin layer chromatography until
the reaction finished. THF was removed under reduced pressure, and the crude product was
obtained. Recrystallization from THF-CH3OH afforded yellow needle crystals. (yield 90%)
m.p. 156–158 ◦C.
Characterization Data of Products
Compound 3a: (diphenylphosphoryl)phenyl methanol9: 1H NMR (400MHz, DMSO-
d6) δ/ppm: 7.79–7.84 (t, J = 9.00 Hz, 4H), 7.46–7.56 (m, 6H), 7.17–7.25 (m, 5H), 6.46–5.51
(dd, JP-H = 6.00 Hz, JH-H = 18.00 Hz, 1H), 5.61 (t, J = 6.20 Hz, 1H); 13C NMR (100 MHz,
DMSO-d6) δ/ppm: 133.84, 132.91, 132.01, 130.97, 130.03, 128.57, 127.84, 73.00; 31P NMR
(162 MHz, DMSO-d6) δ/ppm: 28.3; FTIR (KBr disk) cm−1: νOH 3388, νPO 1162; ESI-MS:
calcd. for 309.1 (M+H)+, 331.1 (M+Na)+; found 308.8(M+H)+, 330.8(M+Na)+.
Compound 3b: (Diphenylphosphoryl)(4-nitrophenyl) methanol7: 1H NMR (DMSO-
d6) δ/ppm: 8.07–8.09 (d, J = 8.00 Hz, 2H), 7.76–7.86 (m, 4H), 7.49–7.58 (m, 8H), 6.80–6.85
(dd, JP-H = 5.60 Hz, JH-H = 16.80 Hz, 1H), 5.85–5.89 (t, J = 7.60 Hz, 1H); 13C NMR
(DMSO-D6) δ/ppm: 147.1, 146.7, 133.1, 132.3, 131.8, 130.9, 128.9, 122.9, 72.4, 71.5; 31P
NMR (DMSO-D6) δ/ppm: 28.7; FTIR (KBr disk) cm−1: νOH 3324, νPO 1172; ESI-MS:
calcd. for 354.08 (M+H)+, 376.08 (M+Na)+; found 353.8 (M+H)+, 375.7 (M+Na)+;
HR-MS: calcd. for C19H16NO4P 354.0895 (M+H)+; found 354.0891 (M+H)+.
Compound 3c: (4-bromophenyl)(Diphenylphosphoryl) methanol: 1H NMR (DMSO-
d6) δ/ppm: 7.77–7.78 (m, 4H), 7.56–7.58 (m, 2H), 7.46–7.55 (m, 4H), 7.38–7.40 (d, J =
8.00 Hz, 2H), 7.17–7.18 (d, J = 6.40 Hz, 2H), 6.55–6.62 (dd, JP-H = 6.00 Hz, JH-H
= 17.6 Hz, 1H), 5.63–5.64 (t, J = 6.60 Hz, 1H); 13C NMR (DMSO-d6) δ/ppm: 138.0,
133.5, 132.5, 130.8, 130.0, 128.8, 128.5, 121.0, 72.2, 71.3; 31P NMR (DMSO-d6) δ/ppm:
28.1; FTIR (KBr disk) cm−1: νOH 3353, νPO 1168; ESI-MS: calcd. for 387.01 (M+H)+,
389.01 (M+H)+; found 386.8 (M+H)+, 388.8 (M+H)+; HR-MS: calcd. for C19H16O2PBr
387.0071 (M+H)+, 389.0051 (M+H)+; found 387.0067 (M+H)+, 389.0048 (M+H)+.
Compound 3d: (Diphenylphosphoryl)(4-methoxyphenyl) methanol: 1H NMR
(DMSO-d6) δ/ppm: 7.49–7.56 (m, 4H), 7.44–7.47 (m, 6H), 7.16–7.18 (d, J = 8.40 Hz,
2H), 6.75–6.77 (d, J = 8.80 Hz, 2H), 6.35–6.41(dd, JP-H = 5.60 Hz, JH-H = 18.00 Hz,
1H), 5.55–5.58 (t, J = 5.40 Hz, 1H), 3.68 (s, 3H); 13C NMR (DMSO-d6) δ/ppm: 133.9,
133.1, 132.3, 131.6, 130.3, 129.4, 128.6, 113.3, 72.4, 55.4; 31P NMR (DMSO-d6) δ/ppm:
28.1; FTIR (KBr disk) cm−1: νOH 3224, νPO 1142; ESI-MS: calcd. for 339.1 (M+H)+,
found 338.8 (M+H)+; HR-MS: calcd. for C20H19O3P 339.1150 (M+H)+; found 339.1146
(M+H)+.
Compound 3e: (Diphenylphosphoryl)(2-methoxyphenyl) methanol: 1H NMR
(DMSO-d6) δ/ppm: 7.17–7.84 (m, 12H), 6.81–6.86 (t, J = 7.20 Hz, 2H), 6.25 (s,1H), 5.95
(s, 1H), 3.47 (s, 3H); 13C NMR (DMSO-d6) δ/ppm: 132.3, 131.3, 129.6, 128.6, 126.6,
120.3, 110.7, 79.6, 65.7, 55.5; 31P NMR (DMSO-d6) δ/ppm: 27.5; FTIR (KBr disk) cm−1
:
νOH 3328, νPO 1176; ESI-MS: calcd. for 339.1 (M+H)+, 361.1 (M+Na)+; found 338.7

REACTION ACTIVITY OF AROMATIC CARBONYL COMPOUNDS
1087
(M+H)+, 360.8 (M+Na)+; HR-MS: calcd. for C20H19O3P 339.1150 (M+H)+; found
339.1147 (M+H)+.
Compound 3f: (Diphenylphosphoryl)(4-hydroxyphenyl) methanol: 1H NMR
(DMSO-d6) δ/ppm: 9.24 (s, 1H), 7.66–7.79 (m, 4H), 7.41–7.51 (m, 6H), 7.01 (d, J =
7.60 Hz, 2H), 6.52 (d, J = 8.40 Hz, 2H), 6.24 (m, 1H), 5.42–5.45 (t, J = 5.20 Hz, 1H);
13C NMR (DMSO-d6) δ/ppm: 157.2, 132.3, 131.7, 129.4, 128.8, 128.5, 114.8, 72.7, 71.8;
31P NMR (DMSO-d6) δ/ppm: 28.1; FTIR (KBr disk) cm−1: νOH 3224, νPO 1132; ESI-MS:
calcd. for 325.09 (M+H)+, found 324.8 (M+H)+; HR-MS: calcd. for C19H17O3P 325.0994
(M+H)+; found 325.0989 (M+H)+.
Compound
3g:
(Diphenylphosphoryl)(2-hydroxyphenyl)
methanol:
1H
NMR(CDCl3) δ/ppm: 9.59 (s, 1H), 7.70–7.81 (m, 4H), 7.41–7.53 (m, 6H), 7.09–7.12 (t,
J = 7.00 Hz, 1H), 6.86–6.95 (dd, JP-H = 8.00 Hz, JH-H = 31.60 Hz, 2H,), 6.67–6.71
(t, J = 7.40 Hz, 1H), 5.64–5.65 (d, J = 5.60 Hz, 1H), 4.07 (s, 1H,); 13C NMR(CDCl3)
δ/ppm: 155.2, 132.5, 132.0, 131.6, 130.6, 129.1, 128.5, 128.0, 127.3, 124.2, 120.5, 119.4,
72.6, 71.8; 31P NMR(CDCl3) δ/ppm: 36.7; FTIR (KBr disk) cm−1: νOH 3228, νPO 1140;
ESI-MS: calcd. for 325.09 (M+H)+, found 324.8 (M+H)+; HR-MS: calcd. for C19H17O3P
325.0994 (M+H)+; found 325.0990 (M+H)+.
Compound 3i: hexa[4-(diphenylphosphoryl hydroxymethyl) phenoxy] cyclotriphos-
1
phazene: H NMR(CDCl3) δ/ppm: 5.48 (s, 6H), 6.35–7.83 (m, 84H); 13C NMR(CDCl3)
δ/ppm: 18.6, 29.7, 71.3, 71.6, 72.7, 119.9, 128.3, 128.9, 129.0, 130.6, 130.7, 130.9, 131.9,
132.3, 133.9, 149.7; 31P NMR(CDCl3) δ/ppm: 9.2, 31.0; FTIR (KBr disk) cm−1: νOH
3334, νPO 1180; ESI-MS: calcd. For 2074.43 (M+H)+, 2096.43 (M+Na)+, found 2074.9
(M+H)+, 2096.8 (M+Na)+; HR-MS: calcd. for C114H96N3O18P9 2074.4406 (M+H)+;
found 2074.4412 (M+H)+.
Synthesis of Compounds 3h
Under the earlier reactive condition, we could not obtain compound 3h; instead, we
get the oxide product of diphenylphosphine oxide, namely diphenylphosphinic acid, which
can also be obtained by the direct oxidation of diphenylphosphine oxide. Only when the
solution was refluxed for an extended period of time, even overnight under nitrogen, was
compound 3h obtained as a white solid.
REFERENCES
1. Sponton, M.; Ronda, J. C.; Galia, M.; Cadia, V. J. Polym. Sci. Part A: Polym. Chem. 2007, 45,
2142-2151.
2. Vecchi, P. A.; Padmaperuma, A. B.; Qiao, H.; Sapochak, L. S.; Burrows, P. E. Org. Lett. 2006,
8, 4211-4214.
3. Padmaperuma, A. B.; Sapochak, L. S.; Burrows, P. E. Chem. Mater. 2006, 18, 2389-2396.
4. Sapochak, L. S.; Padmaperuma, A. B.; Cai, X. Y.; Male, J. L.; Burrows, P. E. J. Phys. Chem. C
2008, 112, 7989-7996.
5. Burrows, P. E.; Padmaperuma, A. B.; Sapochak, L. S. Appl. Phys. Lett. 2006, 88, 183503.
6. Liu, W.-Y.; Huo, P. Acta. Cryst. 2008, E64, O233-U4648.
7. Liu, W.-Y.; Huo, P.; Gao, Y.-X.; Liu, P.; Zhao, Y.-F. Acta. Cryst. 2007, E63, O1008-O1009.
8. Yuan, X.-L.; Liu, W.-Y.; Huo, P.; Mei, G. O. Acta. Cryst. 2010, E66, O2331-U514.
9. Clark, H. J.; Wang, R.; Alper, H. J. Org. Chem. 2002, 67, 6224-6225.
10. Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165-195.
11. Charton, M. J. Org. Chem. 1963, 28, 3121.
12. Shioji, K.; Matsumoto, A.; Takao, M.; Kurauchi, Y.; Shigetomi, T.; Yokomori, Y.; Okuma, K.
Bull. Chem. Soc. Jpn. 2007, 80(4), 743-746.