Superacid-catalyzed Friedel–Crafts phosphination of 2-hydroxybiphenyls with phosphorus trichloride

Article abstract of DOI:10.1002/hc.21346

Cyclic phosphorus compounds, 6H-dibenz[c,e][1,2]oxaphosphorin-6-oxide derivatives, were efficiently synthesized by the Friedel–Crafts reaction of 2-hydroxybiphenyls with phosphorus trichloride in the presence of superacids, especially trifluoromethanesulfonic acid (TfOH) as a catalyst. TfOH was investigated for the first time as an effective catalyst for the aromatic phosphination of 2-hydroxybiphenyls.

Full text of DOI:10.1002/hc.21346

Received: 16 May 2016
DOI: 10.1002/hc.21346
Revised: 21 July 2016
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R E S E A R C H A R T I C L E
Superacid-catalyzed Friedel–Crafts phosphination of
-hydroxybiphenyls with phosphorus trichloride
2
Takatoshi Ito1
Takumi Mizuno
Toshiyuki Iwai1
|
Takeo Nakai1
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Masatoshi Mihara
1
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|
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1
1
2
2
Toshinobu Ohno
Akira Ishikawa
|
Jun-ichi Kobayashi
1Osaka Municipal Technical Research Institute,
Osaka, Japan
2Marubishi Oil Chemical Co., Ltd, Osaka,
Japan
Abstract
Cyclic phosphorus compounds, 6H-dibenz[c,e][1,2]oxaphosphorin-6-oxide deriva-
tives,wereefficientlysynthesizedbytheFriedel–Craftsreactionof2-hydroxybiphenyls
with phosphorus trichloride in the presence of superacids, especially trifluorometh-
anesulfonic acid (TfOH) as a catalyst. TfOH was investigated for the first time as an
effective catalyst for the aromatic phosphination of 2-hydroxybiphenyls.
Correspondence
Takatoshi Ito and Toshinobu Ohno, Osaka
Municipal Technical Research Institute,
Osaka, Japan.
Emails: ito@omtri.or.jp; ohno@omtri.or.jp
with phosphorus trichloride.[
5,6]
In the recent improvement
1
|
INTRODUCTION
of phosphination of aromatic compounds, the use of bis-
muth chloride and bismuth trifluoromethanesulfonate were
6
H-Dibenz[c,e][1,2]oxaphosphorin ring derivatives (Fig. 1)
[7]
revealed as efficient catalysts. These observations pro-
moted us to propose a suitable catalyst and an improvement
in the syntheses of 3. In this letter, we would like to report
are industrially significant compounds for the preparation
of flame retardants, additives for polymerization processes,
photoinitiators, stabilizers for polymers, and photographic
[8]
materials.[1]
superacids catalyzed phosphination of 2-hydroxybiphenyls
with phosphorus trichloride to afford the corresponding 3 in
good to excellent yields. Although various superacids have
been found to catalyze nucleophilic addition of nitrogen,
Numerous patents and literatures have been issued for
the preparation and characterization of 6H-dibenz[c,e][1,2]
oxaphosphorin ring system.
[2,3]
Their synthetic intermediate,
[9]
[10]
oxygen, and sulfur to olefins, Friedel–Crafts acylation,
6
-chloro-6H-dibenz[c,e][1,2]oxaphosphorin (3a) is generally
[11]
and Diels–Alder reaction, to the best of our knowledge, no
superacid-catalyzed phosphination of aromatic compounds
has been hitherto described. As compared with the conven-
tional Lewis acid-catalyzed reaction, the present method in
the presence of superacid is characterized by mild reaction
conditions and metal-free process.
synthesized by the reaction of 2-hydroxybiphenyl (1a) with
[4]
phosphorus trichloride to give the intermediate 2a, fol-
lowed by the Friedel–Crafts type reaction using Lewis acids,
[3]
such as ZnCl , AlCl and FeCl , as catalysts (Scheme 1).
2
3
3
However, in this preparation process of the cyclic phospho-
rus compound 3a, the Lewis acid-catalyzed phosphination
required elevated temperatures which in some case exceeded
to a final temperature of >200°C and were not adequate for
industrial processes.
However, various aryl dichlorophosphine have been pre-
pared by the Friedel–Crafts reaction of aromatic hydrocarbons
Contract grant sponsor: JSPS KAKENHI.
Contract grant number: 25410198.
SCHEME 1 Friedel–Crafts type phosphination reaction
3
36
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© 2016 Wiley Periodicals, Inc.
wileyonlinelibrary.com/journal/hc
Heteroatom Chemistry 2016; 27: 336–342

Ito et al.
337
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2
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RESULTS AND DISCUSSION
of TfOH could enhance the yield and reduce the reaction time
effectively in the preparation of cyclic compounds (Table 1,
entry 5). Moreover, it was revealed that other superacids,
such as nonafluorobutane-1-sulfonic acid (C F SO H) and
First, the Friedel–Crafts reaction of 2-hydroxybiphenyl (1a)
[3e]
was examined by a slightly modified literature procedure.
4
9
3
Brief optimization of the reaction conditions was stud-
bis(trifluoromethane)sulfonimide (Tf NH), also gave 3a in
2
ied using 1a (8.51 g, 50 mmol) and phosphorus trichloride
excellent yield, respectively (Table 1, entries 6 and 7). None
of desired product was obtained in the case of simple Brønsted
acids, such as sulfuric acid, methanesulfonic acid, and trif-
luoroacetic acid. (Table 1, entries 12, 13, and 14). Next, ef-
fects of the reaction temperature and catalyst loading were
investigated. A decrease in the reaction temperature to 120°C,
reduced both the reaction rate and the product yield. However,
it is noteworthy that the yield was improved from 53% to 88%
by carrying out the reaction for longer reaction times (Table 1,
entries 8 and 9). In addition, only 0.15 mol % of the catalyst
showed high catalytic activity (Table 1, entries 10 and 11).
To establish the generality of this method, the reactions of
several 2-hydroxybiphenyls 1a–i with phosphorus trichloride
in the presence of TfOH were examined under the optimized
conditions. 2-hydroxybiphenyls 1b–g and 1i were prepared
according to a literature procedure, using cross-coupling
reaction of the corresponding Grignard reagents with halo-
(
8.58 g, 62.5 mmol) in the presence of various acids as cata-
lysts without solvent. The results are summarized in Table 1.
In the presence of 1.5 mol% of ZnCl , the reaction was carried
out at 150°C and the corresponding phosphorus compound
2
3
a was obtained in 92% yield (Table 1, entry 1). Lowering
the reaction temperature to 120°C decreased the product yield
[7]
(
Table 1, entry 2). In the previous report, BiCl was shown
3
as an effective catalyst for the aromatic phosphination of acti-
vated aromatic compounds compared to the use of commonly
used AlCl . Next we chose BiCl as a catalyst, however, only
3
3
1
4% of 3a was obtained with considerable amount of start-
ing materials (Table 1, entry 3). Use of metal triflates, such as
Zn(OTf) , gave a comparable yield to that of ZnCl (Table 1,
2
2
entry 4). It is well-known that superacid, such as TfOH, ef-
ficiently catalyses the Friedel–Crafts acylation reaction of
acyl chlorides with aromatic compounds. Thus, we tried to
use TfOH as a catalyst in the Friedel–Crafts phosphination.
Consequently, it was found that the reaction in the presence
[
12]
phenols in the presence of palladium catalyst.
The chloro
derivatives 3 can in principle be isolated as exemplified for
TABLE 1 Friedel–Crafts phosphination of 2-hydroxybiphenyl with phosphorus trichloride under various reaction conditionsa
Cl
catalyst
.25 eq. PCl
OH
P
1
3
O
conditions
1a
3a
Entry
Catalyst (mol%)
Temp. (°C)
Time (h)
Yield of 3a (%)b
1
2
3
4
5
6
7
8
9
ZnCl (1.5)
150
120
150
150
150
150
150
120
120
150
180
150
150
150
8
10
4
92
12
2
ZnCl (1.5)
2
BiCl (1.5)
14
3
Zn(OTf) (1.5)
8
90
95 (94)c
3
TfOH (1.5)
4
C F SO H (1.5)
4
95
4
9
3
(CF SO ) NH (1.5)
4
94
3
2 2
TfOH (1.5)
TfOH (1.5)
TfOH (0.15)
TfOH (0.15)
H SO (1.5)
4
53
8
88
10
11
12
13
14
6
80
6
89
4
0
2
4
MeSO H (1.5)
4
0
3
CF CO H (1.5)
4
0
3
2
a
All reactions were carried out by using 2-phenylphenol (50 mmol) with phosphorus trichloride (62.5 mmol) in the presence of various catalysts.
b
c
Yield was determined by the HPLC analysis after hydrolysis of 3a.
Isolated yield of 6H-dibenz[c,e][1,2]oxaphosphorin-6-oxide.

3
38
Ito et al.
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[
3d]
the compound 3a,
(after simple filtration and concentra-
conceivable that the aromatic phosphination of phenols with
tion of reaction mixture, chloro compound 3a is obtained in
considerable yield and purity. 6-chloro-6H-dibenz[c,e][1, 2]
PCl in the presence of TfOH proceeds through in situ gen-
3
+
−
erated PCl (OTf), P Cl + TfO and/or ArO PCl (OTf),
2
2
1
+
−
[5c]
oxaphosphorin (3a). H NMR (300 MHz, CDCl ): δ (ppm)
ArOP Cl + TfO as active species.
3
7
7
1
1
1
.99–7.92 (m, 2 H), 7.69–7.55 (m, 2 H), 7.46–7.33 (m, 2 H),
1
3
.28–7.18 (m, 2 H); C NMR (75.5 MHz, CDCl ): δ (ppm)
3
48.0 (d, J = 10.0 Hz), 132.8 (d, J = 36.7 Hz), 132.8, 131.3,
30.0 (d, J = 10.6 Hz), 129.2, 127.8 (d, J = 13.1 Hz), 124.8,
24.6, 123.9, 122.2 (d, J = 6.9 Hz), 121.0 (d, J = 2.5 Hz);
3
|
CONCLUSION
In summary, 6H-dibenz[c,e][1,2]oxaphosphorin-6-oxide deriv-
atives were efficiently synthesized by the Friedel–Crafts reac-
tion of 2-hydroxybiphenyls with phosphorus trichloride in the
presence of super acids, especially TfOH as a catalyst. TfOH
was investigated for the first time in the present results to prove
to be an effective catalyst. Thus, it was revealed that the super-
acid is effective for the phosphination of 2-phenylbiphenyls.
Elucidation of the detailed reaction mechanism must
await further study.
3
1
P NMR (109 MHz, CDCl ): δ (ppm) 132.8; δ 132.18; ref.
3
[3e]
[
3c]), however, because of their sensitivity to humidity,
they were transformed to the stable oxides 4 after hydrolysis
(
Scheme 2). The results are shown in Table 2.
In the case of 2-hydroxybiphenyls bearing not only
electron-releasing groups but also electron-withdrawing
groups on the phenol ring, the compounds smoothly under-
went to afford the corresponding phosphonated compounds
4
in fair to good yields. The presence of a substituted group
on the aryl ring where electrophilic substitution occurs has
no influence on the regioselectivity of the intramolecular cy-
clization, producing the corresponding products as the unsep-
arable mixture of regioisomers (Table 2, entries 5).
4
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EXPERIMENTAL
Melting points were determined with a Yanako MP-I3 in-
strument (Yanako, Kyoto, Japan) and were uncorrected.
FT-IR spectra were recorded on a JASCO FT/IR-4100 in-
strument. H and C NMR spectra were obtained on a JEOL
JNM-AL300 (300 MHz, 75 MHz) instrument. Chemical
shifts were reported in ppm on the δ scale relative to te-
tramethylsilane (0 ppm) and chloroform-d (77 ppm) as an
internal standard, respectively. P NMR spectra were ob-
tained on a JEOL JNM-EX270 (109 MHz) or JEOL JNM-
ECA600 (243 MHz) spectrometer with complete decoupling.
Chemical shifts were reported in the scale relative to phos-
phoric acid (0 ppm). Mass spectra were measured on a
Shimadzu LCMS-IT-TOF spectrometer.
Recently, bridged 6H-dibenz[c,e][1,2]oxaphosphorin-
6
-oxide derivatives were developed and evaluated as frame
[13]
1
13
retardant having high thermally stability.
Novel bridged
[
14]
derivatives 4j was synthesized from compound 1j
having
two 2-hydroxybiphenyl units on the molecule and 3 equiva-
lent of trichlorophosphine in 74% yield (Scheme 3).
3
1
In the case of the Friedel–Crafts acylation of acyl chlo-
rides with aromatic compounds in the presence of TfOH, it
is assumed that the triflic mixed anhydrides are generated
[10b-d]
in situ as acylating agents.
Although we are unsure
about exact structure of the active reaction species and the
mechanistic details still remain ambiguous at present, it is
4
.1
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The representative procedure
for the preparation of 6H-dibenz[c,e][1,2]
oxaphosphorin-6-oxide (4a) is as follows
In a two-necked round-bottom flask equipped with a re-
flux condenser, 2-phenylphenol (8.51 g, 50 mmol) and trif-
luoromethanesulfonic acid (113 mg, 0.75 mmol) were put
and heated to 150°C. Then, phosphorus trichloride (8.58 g,
FIGURE 1 6H-dibenz[c,e][1,2]oxaphosphorin ring derivatives.
6
3
2.5 mmol) was added dropwise to the mixture for ca.
0 min, so as to maintain a slow reflux of phosphorus trichlo-
ride with a simultaneous evolution of HCl. The reaction mix-
ture was stirred for further 4 hours until no further HCl was
evolved. After the excess of phosphorus trichloride was then
distilled off, the reaction mixture including the chloro com-
pound 3a was then cooled to room temperature and dissolved
in 20 mL of chloroform, followed by the insoluble orange
solid was filtered off and washed with 20 mL of chloroform.
To the filtrate, 10 mL of water was added dropwise (vigorous
SCHEME 2 The tautomeric equilibrium of 6H-dibenz[c,e][1,2]
oxaphosphorin ring

Ito et al.
339
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TABLE 2 Trifluoromethanesulfonic acid-catalyzed Friedel–Crafts phosphination of various 2-hydroxybiphenyls with phosphorus trichloride
O
H
OH
P
Y
O
1.5 mol% TfOH
H O
2
Y
1
.25 eq. PCl3
X
o
X
150 C 4 h
1
Substrate
OH
4
Entry
1a
Product
Yield (%)d
O
H
94
P
O
1a
4a
2b
90
81
Me
O
H
OH
P
Me
O
1b
4b
3c
O
H
OH
P
O
Me
1c
Me
4c
4c
88
O
H
OH
P
O
1d
Cl
4d
Cl
5c
6c
7c
90e
75
O
H
OH
P
O
Me
Me
1
e
4e
OMe
O
H
OH
P
OMe
O
1
f
4f
80
O
H
P
OH
O
1g
4g
Continued

3
40
Ito et al.
|
TABLE 2 Continued
Entry
Substrate
Product
Yield (%)d
8c
73
O
H
OH
P
O
1h
4h
9c
81
O
O
H
OH
P
O
O
1i
4i
a
Reaction was carried out by using 2-hydroxybiphenyl (50 mmol) with phosphorus trichloride (62.5 mmol) at 150°C for 4 hours in the presence of 1.5 mol% of TfOH.
b
Reactions were carried out by using 2-hydroxybiphenyls (10 mmol) with phosphorus trichloride (12.5 mmol) at 150°C for 4 hours in the presence of 1.5 mol% of TfOH.
Reactions were carried out by using 2-hydroxybiphenyls (1 mmol) with phosphorus trichloride (1.5 mmol) at 150°C for 6 hours in the presence of 5.0 mol% of TfOH in
c
1
,2-dichlorobenzene (3 mL).
Isolated yield.
d
e
The regioisomeric mixtures of the products were obtained with ca. 3:2.
SCHEME 3 Synthesis of bridged 6H-dibenz[c,e][1,2]oxaphosphorin-6-oxide derivative
HCl formation) very carefully. After evaporation of the sol-
vent under reduced pressure, residual water was removed by
azeotropic distillation with toluene for 2 hours. The solution
was concentrated and the residue dried under vacuum to give
analytically pure 4a in 10.1 g (94%) yield. Their derivatives 4
can be further purified by recrystallization or gel permission
3H), 7.78–7.72 (m, 1H), 7.59–7.51 (m, 1H). 7.44–7.38 (m,
1
3
1H) 7.32–7.26 (m, 2H); C NMR (75.5 MHz, CDCl ): δ
3
(ppm) 148.2 (d, J = 8.7 Hz), 135.9 (d, J = 6.9 Hz), 134.1
(d, J = 2.5 Hz), 130.9, 130.6 (d, J = 12.5 Hz), 128.7 (d,
J = 14.3 Hz), 125.2, 125.1, 124.0 (d, J = 9.9 Hz), 123.5 (d,
J = 122.0 Hz), 122.0 (d, J = 12.5 Hz), 120.7 (d, J = 6.2 Hz);
[2d–f,3d]
31
chromatography, if necessary.
P NMR (109 MHz, CDCl ): δ (ppm) 15.13; DART-HRMS
3
+
The intermediated chloro compound 3a, 6-chloro-6H-
dibenz[c,e][1, 2] oxaphosphorin, is obtained after simple
filtration and concentration of reaction mixture in consider-
able yield and purity. H NMR (300 MHz, CDC ): δ (ppm)
calcd for C H O P [M+H] : 217.0413; found 217.0438.
1
2 10 2
4
.1.2
|
8-Methyl-6H-dibenz[c,e][1,2]
1
l3
oxaphosphorin-6-oxide (4b)
7
7
1
1
1
.99–7.92 (m, 2 H), 7.69–7.55 (m, 2 H), 7.46–7.33 (m, 2 H),
−
1
.28–7.18 (m, 2 H); C NMR (75.5 MHz, CDC ): δ (ppm)
White solid, 90% yield, mp 124–126°C; IR (KBr, cm ):
1
3
l3
1
48.0 (d, J = 10.0 Hz), 132.8 (d, J = 36.7 Hz), 132.8, 131.3,
30.0 (d, J = 10.6 Hz), 129.2, 127.8 (d, J = 13.1 Hz), 124.8,
ν 2431 (P-H), 1479, 1230, 917, 760; H NMR (300 MHz,
CDCl ): δ (ppm) 8.00 (d, J = 590.4 Hz, 1H), 7.99–7.85 (m,
3
24.6, 123.9, 122.2 (d, J = 6.9 Hz), 121.0 (d, J = 2.5 Hz);
P
1
2H), 7.66 (d, J = 15.0 Hz, 1H), 7.48 (d, J = 8.1 Hz, 1H),
7.33 (d, J = 8.4 Hz, 1H), 7.21 (t, J = 5.7 Hz, 2H), 2.40
3
NMR (109 MHz, CDC ): δ (ppm) 132.8; δ 132.18; ref. [3c].
l3
1
3
(
s, 3H); C NMR (75.5 MHz, CDCl ): δ (ppm) 147.8 (d,
3
J = 8.7 Hz), 138.7 (d, J = 14.2 Hz), 134.8 (d, J = 2.5 Hz),
4
.1.1
|
6H-dibenz[c,e][1,2]oxaphosphorin-6-
1
1
32.8 (d, J = 6.8 Hz), 130.5 (d, J = 12.4 Hz), 130.1, 124.8,
oxide (4a)
24.7, 122.2, 121.7 (d, J = 12.5 Hz), 120.2 (d, J = 6.2 Hz),
−
1
31
White solid, 94% yield, mp 114–116°C; IR (KBr, cm ): ν
20.9; P NMR (243 MHz, CDCl ): δ (ppm) 15.86; DART-
3
1
+
2
384 (P-H), 1592, 1448, 1151, 1076; H NMR (300 MHz,
HRMS calcd for C H O P [M+H] : 231.0569; found
1
3 12 2
CDCl ): δ (ppm) 8.06 (d, 1H, J = 591.6 Hz), 7.99–7.86 (m,
231.0563.
3

Ito et al.
341
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4
.1.3
|
2-Methyl-6H-dibenz[c,e][1,2]
4.1.6
|
8-Methoxy-6H-dibenz[c,e][1,2]
oxaphosphorin-6-oxide (4c)
oxaphosphorin-6-oxide (4f)
−
1
−1
Pale yellow solid, 81% yield, mp 98–101°C; IR (KBr, cm ):
White solid, 75% yield, mp 144–147°C; IR (KBr, cm ): ν 2370
1
1
ν 2409 (P-H), 1228, 1209, 903, 491; H NMR (300 MHz,
(P-H), 1606, 1475, 1227, 1207; H NMR (300 MHz, CDCl ): δ
3
CDCl ): δ (ppm) 8.00 (d, J = 589.2 Hz, 1H), 7.99–7.85
(ppm) 8.00 (d, J = 591.3 Hz, 1H), 7.99–7.70 (m, 2H), 7.40–7.25
3
13
(
(
(
m, 2H), 7.78–7.68 (m, 2H), 7.58–7.51 (m, 1H), 7.28–7.12
(m, 2H), 7.23–7.15 (m, 3H), 385 (s, 3H); C NMR (75.5 MHz,
1
3
m, 2H), 2.41 (s, 3H); C NMR (75.5 MHz, CDCl ): δ
CDCl ): δ (ppm) 159.4 (d, J = 17.4 Hz), 147.3 (d, J = 8.1 Hz),
3
3
ppm) 146.0 (d, J = 8.7 Hz), 136.0 (d, J = 6.9 Hz), 134.6,
129.5, 128.1 (d, J = 6.2 Hz), 125.6 (d, J = 11.9 Hz), 124.8,
124.3, 124.2 (d, J = 120.7 Hz), 121.7 (d, J = 33.6 Hz), 121.2 (d,
J = 2.4 Hz), 120.1 (d, J = 6.3 Hz), 113.1 (d, J = 14.2 Hz), 55.5;
1
33.9 (d, J = 2.5 Hz), 131.5, 130.5 (d, J = 12.4 Hz), 128.4
(
d, J = 14.3 Hz), 125.3, 123.8 (d, J = 9.4 Hz), 123.6 (d,
3
1
J = 122.5 Hz), 121.6 (d, J = 12.4 Hz), 120.3 (d, J = 6.2 Hz),
P NMR (243 MHz, CDCl ): δ (ppm) 15.76; DART-HRMS
3
3
1
+
2
0.94; P NMR (243 MHz, CDCl ): δ (ppm) 15.76; DART-
calcd for C H O P [M+H] : 247.0519; found 247.0543.
3
13 12 3
+
HRMS calcd for C H O P [M+H] : 231.0569; found
1
3 12 2
2
31.0589.
4
.1.7
|
8-Phenyl-6H-dibenz[c,e][1,2]
oxaphosphorin-6-oxide (4 g)
4
.1.4
|
2-Chloro-6H-dibenz[c,e][1,2]
−1
White solid, 80% yield, mp 60–64°C; IR (KBr, cm ): ν 2370
oxaphosphorin-6-oxide (4d)
1
(
P-H), 1473, 1234, 1204, 957, 913; H NMR (300 MHz,
White solid, 88% yield, mp 129–131°C; IR (KBr,
cm ): ν 3068, 2371 (P-H), 1477, 1223, 903; H NMR
CDCl ):δ(ppm)8.08(d,J = 592.2 Hz,1H),8.15–7.80(m, 4H),
3
−
1
1
7.70–7.60 (m, 2H), 7.55–7.35 (m, 4H), 7.30–7.21 (m, 2H);
1
3
(
300 MHz, CDCl ): δ (ppm) 8.06 (d, J = 602.7 Hz, 1H),
C NMR (75.5 MHz, CDCl ): δ (ppm) 148.1 (d, J = 8.1 Hz),
3
3
7
1
.95–7.83 (m, 3H), 7.79–7.73 (m, 1H), 7.61–7.54 (m,
141.4 (d, J = 14.3 Hz), 138.6, 134.4 (d, J = 6.3 Hz), 132.4,
130.7, 129.0, 128.7 (d, J = 13.1 Hz), 128.3, 126.8, 125.1,
125.0, 124.4 (d, J = 10.6 Hz), 123.8 (d, J = 196.7 Hz), 121.7
1
3
H), 7.40–7.32 (m, 1H), 7.20 (d, J = 8.7 Hz); C NMR
(
(
1
1
75.5 MHz, CDCl ): δ (ppm) 146.4 (d, J = 8.7 Hz), 134.5
3
31
d, J = 6.9 Hz), 134.4 (d, J = 2.5 Hz), 130.8, 130.6, 130.6,
(d, J = 11.8 Hz), 120.5 (d, J = 6.3 Hz); P NMR (243 MHz,
CDCl ): δ (ppm) 15.53. DART-HRMS calcd for C H O P
29.3 (d, J = 14.3 Hz), 125.0, 124.2 (d, J = 110.2 Hz),
24.0 (d, J = 9.9 Hz), 123.1 (d, J = 12.5 Hz), 121.9 (d,
3
18 14 2
+
[M+H] : 293.0726; found 293.0751.
3
1
J = 6.2 Hz); P NMR (243 MHz, CDCl ): δ (ppm) 15.18;
3
+
DART-HRMS calcd for C H ClO P [M+H] : 251.0023;
1
2
9
2
4
.1.8
|
4-Phenyl-6H-dibenz[c,e][1,2]
found 251.0005.
oxaphosphorin-6-oxide (4 h)
−
1
White solid, 73% yield, mp 157–159°C; IR (KBr, cm ): ν
4
.1.5
|
Mixture (ca. 3: 2) of 7-Methyl-6H-
1
2
370 (P-H), 1410, 1229, 1211, 1189; H NMR (300 MHz,
dibenz[c,e][1,2]oxaphosphorin-6-oxide
and 9-Methyl-6H-dibenz[c,e][1,2]
oxaphosphorin-6-oxide (4e)
CDCl ): δ (ppm) 7.97 (d, 1H, J = 593.7 Hz), 8.05–7.97
3
(
(
m, 1H), 7.96–7.83 (m, 2H), 7.79–7.69 (m, 1H), 7.62–7.51
13
m, 3H), 7.50–7.29 (m, 5H); C NMR (75.5 MHz, CDCl ):
3
−1
δ (ppm) 144.7 (d, J = 8.8 Hz), 136.4 136.0 (d, J = 6.3 Hz),
White solid, 90% yield; IR (KBr, cm ): ν 2400 (P-H), 1606,
1
1
33.9 (d, J = 2.5 Hz), 133.8 (d, J = 5.6 Hz), 132.2, 130.2
d, J = 13.7 Hz), 129.5, 128.5 (d, J = 14.3 Hz), 128.3,
27.7, 124.9, 124.5, 124.5, 123.6 (d, J = 115.1 Hz), 122.6
1
488, 1456, 1440, 1228; H NMR (300 MHz, CDCl ): δ
3
(
(
ppm) 8.46 (d, J = 600.3 Hz, 0.7H), 8.03 (d, J = 589.4 Hz,
1
0
7
.3H), 7.94–7.74 (m, 2.3H), 7.6 (t, J = 7.5 Hz, 0.7H),
3
1
1
3
(
d, J = 11.8 Hz); P NMR (109 MHz, CDCl ): δ (ppm)
.43–7.23 (m, 4H), 2.72 (s, 2.1H), 2.50 (s, 0.9H); C NMR
3
1
4.50, ref. [3d] δ 14.5. DART-HRMS calcd for C H O P
18 14 2
(
75.5 MHz, CDCl ): δ (ppm) 148.3 (d, J = 8.4 Hz), 147.8 (d,
3
+
[M+H] : 293.0726; found 293.0725.
J = 8.7 Hz), 144.8 (d, J = 2.5 Hz), 140.7 (d, J = 12.3 Hz),
35.9 (d, J = 6.8 Hz), 135.6 (d, J = 4.9 Hz), 133.4 (d,
1
J = 1.9 Hz), 130.8, 130.7, 130.5, 130.5, 130.4, 130.3, 129.5
4
.1.9
|
8-Phenoxy-6H-dibenz[c,e][1,2]
(
(
d, J = 14.9 Hz), 1258.4, 125.0 (d, J = 8.0 Hz), 124.9, 124.5
d, J = 5.7 Hz), 121.8 (d, J = 12.5 Hz), 121.7 (d, J = 9.3 Hz),
oxaphosphorin-6-oxide (4i)
−1
1
20.6 (d, J = 6.3 Hz), 120.4 (d, J = 5.6 Hz), 22.2, 19.7 (d,
White solid, 81% yield, mp 63–66°C; IR (KBr, cm ): ν 2367
3
1
1
J = 10.0 Hz); P NMR (243 MHz, CDCl ): δ (ppm) 14.84;
(P-H), 1587, 1488, 1259, 1223, 757; H NMR (300 MHz,
3
+
DART-HRMS calcd for C H O P [M+H] : 231.0569;
CDCl ):δ(ppm)7.97(d,1H,J = 595.2 Hz),7.95–7.80(m, 2H),
3
1
3
12
2
1
3
found 231.0593.
7.45–7.30 (m, 5H), 7.30–7.15 (m, 3H), 7.10–7.05 (m, 2H); C

3
42
Ito et al.
|
J. Y. Shieh, Polymer 1998, 39, 5819; f) Y. L. Liu, S. H. Tsai, Polymer 2002,
NMR (75.5 MHz, CDCl ): δ (ppm) 158.1 (d, J = 18.0 Hz),
3
4
3, 5757.
1
1
1
55.4, 147.6 (d, J = 8.7 Hz), 130.3, 130.0 (d, J = 6.2 Hz),
26.1 (d, J = 11.2 Hz), 125.1, 124.8 (d, J = 119.4 Hz),
24.7, 124.0 (d, J = 3.1 Hz), 121.7 (d, J = 12.6 Hz), 120.5
[
[
2] a) T. Saito, U S Pat 3 1972, 702, 878; b) T. Saito, T. Hirayama, Y. Kohguchi,
U S Pat 6 2000, 107, 506; c) H.-J. Kleiner, U S Pat 5 1995, 391, 798 and 5,
1996, 481, 017; d) P. Rathfelder, H. Rieckert, J. Dietrich, U S Pat 5 1998,
821, 376; e) H. Takeuchi, M. Sato, S. Gyobu, U S Pat 6 2001, 245, 880; f)
H. J. Kleiner, U S Pat 5 1996, 481, 17.
3] a) K. A. Salmeia, S. Gaan, Polym. Degrad. Stab. 2015, 113, 119; b) E.
A. Chernyshev, V. I. Aksenov, V. V. Ponmarev, S. A. Golubtsov, E. F.
Bugerenko, J. Gen. Chem. 1972, 42, 88; c) T. K. Prakasha, R. O. Day, R. R.
Holmes, J. Am. Chem. Soc. 1994, 116, 8095; d) S. D. Pastor, J. D. Spivack,
L. P. Steinhuebel, Phosphorus Sulfur 1987, 31, 71; e) A. Qureshi, A. S. Hay,
J. Chem. Res. (m). 1998, 1601.
3
1
(
d, J = 6.3 Hz), 119.9, 118.4 (d, J = 13.7 Hz); P NMR
(
243 MHz, CDCl ): δ (ppm) 14.65. DART-HRMS calcd for
3
+
C H O P [M+H] : 309.0675; found 309.0702.
13 14 3
4
.1.10
|
2,2′-(1,10-decanediyl)-bis(6H-
dibenz[c,e][1,2]oxaphosphorin-6-oxide) (4j)
[
[
4] H. Tolkmith, J. Org. Chem. 1958, 23, 1682.
−1
White solid, 71% yield, mp 133–136°C; IR (KBr, cm ): ν
5] a) B. Buchner, L. B. Lockhart Jr, J. Am. Chem. Soc. 1951, 73, 755; b) I.
Granoth, Y. Segall, A. Kalir, J. Chem. Soc. Perkin Trans. I 1973, 1972; c) Z.
W. Wang, L. S. Wang, Green Chem. 2003, 5, 737.
1
2
923, 2361 (P-H), 1233, 1211, 910; H NMR (300 MHz,
CDCl ): δ (ppm) 7.99 (d, 1H, J = 589.8 Hz), 7.99–7.80 (m,
3
[
[
6] J. Emsley, D. Hall, The Chemistry of Phosphorus, Harper and Row, London
4
H), 7.78–7.65 (m, 4H), 7.55–7.41 (m, 2H), 7.20–7.12 (m,
1
976.
4
H), 2.64 (d, J = 7.8 Hz, 4H), 1.626 (br, 4H), 1.31 (br, 12H);
7] F. Siméon, P. A. Jaffrés, D. Villemin, Tetrahedron 1998, 54, 10111.
1
3
C NMR (75.5 MHz, CDCl ): δ (ppm) 145.9 (d, J = 8.1 Hz),
[8] a) G. A. Olah, G. K. S. Prakash, J. Sommer, Superacids, John Wiley & Sons,
New York 1985; b) H. Yamamoto, K. Ishihara, Acid Catalysis in Modern
Organic Synthesis, Wiley-VCH, Weinheim 2008.
3
1
39.5, 135.8 (d, J = 6.8 Hz), 133.8 (d, J = 2.5 Hz), 130.1,
30.3 (d, J = 12.5 Hz), 128.2 (d, J = 14.3 Hz), 124.6, 123.7 (d,
1
[
9] a) B. Schlummer, J. F. Hartwig, Org. Lett. 2002, 4, 1471; b) T. C. Wabnitz,
J. B. Spencer, Org. Lett. 2003, 5, 2141; c) Z. Li, J. Zhang, C. Brouwer, C. G.
Yang, N. W. Reich, C. He, Org. Lett. 2006, 8, 4175; d) K. P. Kalbarczyk, S.
T. Diver, J. Org. Chem. 2009, 74, 2193.
[10] a) F. Effenberger, F. Buckel, A. H. Maier, J. Schmider, Synthesis 2000,
000, 1427; b) B. Hulin, M. Koreeda, J. Org. Chem. 1984, 49, 207; c) F.
J = 9.4 Hz), 123.3 (d, J = 122.5 Hz), 121.4 (d, J = 12.4 Hz),
3
1
1
20.1 (d, J = 6.9 Hz), 35.3, 31.3, 29.4, 29.6, 29.0; P NMR
(
243 MHz, CDCl ): δ (ppm) 15.67. DART-HRMS calcd for
3
+
C H O P [M+H] : 571.2167; found 571.2164.
34 37 4 2
2
Effenberger, G. Epple, Angew. Chem. Int. Ed. Engl. 1972, 11, 299; d) F.
Effenberger, E. Sohn, G. Epple, Chem. Ber. 1983, 116, 1195; e) J. P. Hwang,
G. K. S. Prakash, G. A. Olah, Tetrahedron 2000, 56, 7199.
ACKNOWLEDGMENT
[
[
[
11] D. Nakashima, H. Yamamoto, Org. Lett. 2005, 7, 1251.
12] N. A. Bumagin, E. V. Luzikova, J. Organomet. Chem. 1997, 532, 271.
13] A. Buczko, T. Stelzig, L. Bommer, D. Rentsch, M. Heneczkowski, S. Gaan,
Polym. Degrad. Stab. 2014, 107, 158.
This research was supported in part by JSPS KAKENHI
Grant Number 25410198. We thank Mr. Shuhei Takahashi
for the preparation of 2,2′-(1,10-decanediyl)-bis(6H-dibenz[
c,e][1,2]oxaphosphorin-6-oxide).
[14] A. Ciogli, A. D. Cort, F. Gasparrini, F. Lunazzi, L. Mandolini, A. Mazzanti,
C. Pasquini, M. Pierini, L. Schiaffino, F. Mihan, J. Org. Chem. 2008, 73,
6
108.
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Additional Supporting Information may be found online in
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4
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