Synthesis of novel piperazine phosphoramidate analogues of 2-arylquinolones

Article abstract of DOI:10.1080/10426500903120750

A series of novel piperazine phosphoramidate derivatives of 2-arylquinolones were synthesized to improve their physicochemical and biological properties through a facile phosphorylating reaction. Their structures were elucidated by NMR, ESI MS, and HRMS. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/10426500903120750

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Phosphorus, Sulfur, and Silicon and the
Related Elements
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Synthesis of Novel Piperazine
Phosphoramidate Analogues of 2-
Arylquinolones
Zhibo Qu a , Xiaolan Chen a , Lingbo Qu a b , Jinwei Yuan b , Huina Li
a & Yufen Zhao a c
a Key Laboratory of Organic Chemistry and Chemical Biology,
Henan Province, Department of Chemistry , Zhengzhou University ,
Zhengzhou, P. R. China
b School of Chemistry & Chemical Engineering , Henan University of
Technology , Henan Province, Zhengzhou, P. R. China
c Key Laboratory for Bioorganic Phosphorus Chemistry and Chemical
Biology, Ministry of Education, Department of Chemistry, School of
Life Sciences and Engineering , Tsinghua University , Beijing, P. R.
China
Published online: 02 Jul 2010.
To cite this article: Zhibo Qu , Xiaolan Chen , Lingbo Qu , Jinwei Yuan , Huina Li & Yufen Zhao (2010)
Synthesis of Novel Piperazine Phosphoramidate Analogues of 2-Arylquinolones, Phosphorus, Sulfur, and
Silicon and the Related Elements, 185:7, 1516-1520, DOI: 10.1080/10426500903120750
To link to this article: http://dx.doi.org/10.1080/10426500903120750
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Phosphorus, Sulfur, and Silicon, 185:1516–1520, 2010
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500903120750
SYNTHESIS OF NOVEL PIPERAZINE PHOSPHORAMIDATE
ANALOGUES OF 2-ARYLQUINOLONES
Zhibo Qu,1 Xiaolan Chen,1 Lingbo Qu,1,2 Jinwei Yuan,2
Huina Li,1 and Yufen Zhao1,3
1Key Laboratory of Organic Chemistry and Chemical Biology, Henan Province,
Department of Chemistry, Zhengzhou University, Zhengzhou, P. R. China
2School of Chemistry & Chemical Engineering, Henan University of Technology,
Henan Province, Zhengzhou, P. R. China
3Key Laboratory for Bioorganic Phosphorus Chemistry and Chemical Biology,
Ministry of Education, Department of Chemistry, School of Life Sciences and
Engineering, Tsinghua University, Beijing, P. R. China
A series of novel piperazine phosphoramidate derivatives of 2-arylquinolones were synthe-
sized to improve their physicochemical and biological properties through a facile phospho-
rylating reaction. Their structures were elucidated by NMR, ESI MS, and HRMS.
Keywords 2-Arylquinolones; piperazine phosphoramidate; synthesis
INTRODUCTION
2-Arylquinolones are a class of molecules used as aza analogues of flavones. Con-
sequently, synthesis and structural modification of the derivatives of 2-arylquinolone have
attracted much interest. Pharmacological research has demonstrated that 2-arylquinolones
exhibit many important physiological activities, to act as potent cytotoxic, antimitotic,
antibacterial, and antiplatelet agents, and have cardiovascular protecting properties.1–4
The introduction of a phosphate group essentially changes the physical and chemical
properties of the parent molecule, resulting in changes of the polarization and intermolec-
ular bonding characteristics.5–7 Moreover, phosphates and phosphoramidates have been
widely used as prodrug moieties to enhance the water solubility and have proven to be
exceedingly important agents for anticancer and antiviral therapy.8–13 Piperazines also ex-
hibits many physiological activities. They can act as platelet-activating factor antagonists,
potential antipsychotic agents, dopamine transporter inhibitors, and antitumor agents.14–17
Our interest was to synthesize a series of phosphoryl piperazine linked 2-arylquinolone
derivatives to improve their physicochemical and biological properties. A novel type of
Received 2 March 2009; accepted 11 June 2009.
The authors would like to thank the Chinese National Science Foundation (No. 20472076) and Henan
Academic Foundation of Science and Technology (No. 0512001400) for their financial support.
Address correspondence to Xiaolan Chen and Yufen Zhao, Department of Chemistry, Zhengzhou University,
75 Daxue Road, Henan Province, Zhengzhou 450052, P.R. China. E-mail: chenxl@zzu.edu.cn
1516

PIPERAZINE PHOSPHORAMIDATE ANALOGUES OF 2-ARYLQUINOLONES
1517
Cl
K2CO3, Reflux
H
N
R
1
+
HCl HN
2
HCl HN
N
R
1
CH3(CH2)3OH
1
Cl
R
2
R
2
HCl HN
N
R
1
O
O
1
R
2
O
P
Cl
N
N
R
1
O
P
NEt3, -78 oC, CH2Cl2
Cl
Cl
2
3
R
2
3'
2'
R
3
R
3
R
3
1
H
N
8
H
CO
N
3
1'
H
CO
H
CO
3
N
4'
3
7
9
2
5'
OH
3
OCH
6'
O
3
OCH
4'
4
3
6
10
5
4
NEt3, reflux, THF
6''
5''
11
13
5'''
6'''
12
OCH
O
P
3
1''
O
N
N
R
1
4'''
4''
1'''
O
14
2''
3''
2'''
3'''
5
R
2
5
a
b
c
d
e
f
R1
R2
R3
H
H
H
H
H
H
H
Cl
H
Cl
H
Cl
H
CH3
CH3
CH3
CH3
Cl
Scheme 1 Synthesis of piperazine phosphoramide analogues of 2-arylquinolones 5a–f.
phosphoramidate derivatives of 2-arylquinolones was synthesized by a facile phosphory-
lating reaction (Scheme 1).
RESULTS AND DISCUSSION
To synthesize the piperazine phosphoramidate analogues of 2-arylquinolones (5)
(Scheme 1), bis(β-chloroethyl)amine hydrochloride, the arylamine, and potassium carbon-
ate were refluxed in n-butyl alcohol for 28 h. The solid was filtered off. The crystalline
N-arylpiperazine (1) was obtained after the filtrate was cooled down to room temperature.
Phenyl dichlorophosphates (2) were coupled with different N-arylpiperazine to achieve
phenyl aminophosphorochloridates (3), which were used without further purification. 2-
Arylquinolones (4) were reacted with the phenyl aminophosphorochloridates (3) in the
presence of triethylamine in THF to form the piperazine phosphoramide analogues of 2-
arylquinolones (5). The 2-arylquinolones (4) were expected to experience tautomerization
to their 4-hydroquinol isomers (4ꢁ) under basic conditions. The structures of all newly
synthesized 2-arylquinolone derivatives were confirmed by ESI MS, HRMS, and NMR.

1518
Z. QU ET AL.
EXPERIMENTAL
All experiments involving water-sensitive compounds were conducted under scrupu-
1
lously dry conditions. H, 13C, and 31P NMR spectra were recorded on a Bruker Avance
DPX spectrometer operating at 400.13, 100.61, and 161.98 MHz, respectively, with 13C and
31P spectra being recorded proton-decoupled. All NMR spectra were recorded in CDCl3 at
room temperature (20 3◦C). 1H and 13C chemical shifts are quoted in ppm downfield from
TMS. 31P chemical shifts are quoted in ppm relative to an external 85% H3PO4 standard.
Coupling constants J are given in Hz, and the signal splitting patterns are described as
singlet (s), doublet (d), triplet (t), quartet (q), multiplet (m), or combinations thereof. TLC
was performed on silica gel plates and preparative chromatograph on columns of silica gel
(200–300 mesh). HRMS were recorded on a Q-Tof Micro spectrometer.
N-Arylpiperazine (1)
Bis(β-chloroethyl)amine hydrochloride (6.4 g, 0.0358 mol), arylamine (3.2 mL,
0.0358 mol), and K2CO3 (5.0 g) were refluxed in n-butanol (60 mL) for 28 h. The excess
of K2CO3 was filtered off, then the solvent was cooled to room temperature and the N-
arylpiperazine (1) was crystallized.
Phosphochloridate (3)
The phosphodichloridate (2) (1.05 g, 5.0 mmol) and the N-arylpiperazine (1) (1.0
g, 5.0 mmol) were suspended in anhydrous dichloromethane (30 mL). Anhydrous NEt3
(1.4 mL, 10.0 mmol) was added dropwise at –50◦C during 10 min, and then the reaction
mixture was left to rise to room temperature. After 8 h, the solvent was evaporated under
reduced pressure, and the residue was washed with anhydrous ether and filtered. The filtrate
was evaporated to dryness under reduced pressure. The crude phosphochloridate (3) was
obtained and used without further purification.18
Piperazine Phosphoramidate Analogues of 2-Arylquinolones (5)
Anhydrous NEt3 (0.4mL, 3 mmol) was addeddropwisetoasolutionof theappropriate
phosphorochloridate (3) (0.9 g, 2.7 mmol) and 2-arylquinolone (4) (0.5 g, 1.8 mmol) in
anhydrous THF at room temperature. The reaction mixture was refluxed for 6–10 h and
then cooled to room temperature. The precipitated NHEt3Cl was filtered off, and the filtrate
was evaporated under reduced pressure to give the residues as yellow powders. The crude
product (5) was purified by column chromatography on silica gel (cyclohexane:AcOEt,
1:2).
Compound 5a. Yellow powder, mp 147–148◦C, yield 41%. HRMS 582.2157 [M
1
3
+ H]+ (calculated for C33H32N3O5P 581.2080). H NMR: δ 3.04 (t, 4 H, JP-H = 4.8,
H-11/13), 3.48–3.54 (m, 4 H, H-12/14), 3.89 (s, 3 H, 7-OCH3), 3.95 (s, 3 H, 5-OCH3),
6.53 (d, 1 H, JH-H = 2.3, H-6), 6.84–6.89 (m, 3 H, H-2ꢁꢁ/4ꢁꢁ/6ꢁꢁ), 7.12 (d, 1 H, JH-H
=
4
4
2.3, H-8), 7.15–7.17 (m, 1 H, H-4ꢁꢁꢁ), 7.18–7.26 (m, 2 H, H-3ꢁꢁꢁ/5ꢁꢁꢁ), 7.29–7.36 (m, 4 H,
H-3ꢁꢁ/5ꢁꢁ/2ꢁꢁꢁ/6ꢁꢁꢁ), 7.42–7.50 (m, 3 H, H-3ꢁ/4ꢁ/5ꢁ), 7.89 (d, 1 H, 4JP-H = 1.3, H-3), 8.09–8.10
(m, 1 H, H-2ꢁ), 8.09–8.10 (m, 1 H, H-6ꢁ). 13C NMR: δ: 44.7 (C-12/14, d, 3JP-C = 1.7), 49.7
(C-11/13, d, 2JP-C = 5.6), 55.7 (7-OCH3), 55.9 (5-OCH3), 99.4 (C-6), 100.9 (C-8), 107.1
(C-3, d, JP-C = 3.0), 108.4 (C-10, d, JP-C = 6.6), 116.7 (C-2ꢁꢁ/6ꢁꢁ), 120.2 (C-2ꢁꢁꢁ/6ꢁꢁꢁ, d,
3
3

PIPERAZINE PHOSPHORAMIDATE ANALOGUES OF 2-ARYLQUINOLONES
1519
3JP-C = 5.1), 120.5 (C-4ꢁꢁ), 125.1 (C-4ꢁꢁꢁ), 127.5 (C-2ꢁ/6ꢁ), 128.8 (C-3ꢁ/5ꢁ), 129.2 (C-3ꢁꢁ/5ꢁꢁ),
129.6 (C-4ꢁ), 129.8 (C-3ꢁꢁꢁ/5ꢁꢁꢁ), 138.8 (C-1ꢁ), 150.8 (C-1ꢁꢁꢁ, d, 2JP-C = 6.7), 151.2 (C-1ꢁꢁ),
153.6 (C-9), 155.5 (C-4, d, 2JP-C = 6.9), 156.7 (C-5), 158.8 (C-2), 161.4 (C-7). 31P NMR:
δ –2.88.
Compound 5b. Yellow powder, mp 151–152◦C, yield 49%. HRMS 596.2312 [M
+ H]+ (calculated for C34H34N3O5P 595.2236). 1H NMR: δ 2.40 (s, 3 H, 4ꢁ-CH3), 3.03 (t,
4 H, 3JP-H = 4.8, H-11/13), 3.47–3.52 (m, 4 H, H-12/14), 3.87 (s, 3 H, 7-OCH3), 3.94 (s, 3
H, 5-OCH3), 6.51 (d, 1 H, 4JH-H = 2.2, H-6), 6.82–6.88 (m, 3 H, H-2ꢁꢁ/4ꢁꢁ/6ꢁꢁ), 7.11 (d, 1 H,
4JH-H = 2.2, H-8), 7.16–7.18 (m 1 H, H-4ꢁꢁꢁ), 7.27–7.36 (m, 6 H, H-2ꢁꢁꢁ/3ꢁꢁꢁ/5ꢁꢁꢁ/6ꢁꢁꢁ/3ꢁꢁ/5ꢁꢁ),
4
3
7.20–7.25 (m, 2 H, H-3ꢁ/5ꢁ), 7.88 (d, 1 H, JP-H = 1.3, H-3), 8.00 (d, JH-H = 4.1, 1 H,
H-2ꢁ), 8.02 (d, 3JH-H = 4.1, 1 H, H-6ꢁ). 13C NMR: δ 44.7 (C-12/14), 49.7 (C-11/13, d, 2JP-C
3
= 5.5), 55.6 (7-OCH3), 55.9 (5-OCH3), 99.3 (C-6), 100.9 (C-8), 106.9 (C-3, d, JP-C
=
3.0), 108.3 (C-10, d, 3JP-C = 6.7), 116.7 (C-2ꢁꢁ/6ꢁꢁ), 120.2 (C-2ꢁꢁꢁ/6ꢁꢁꢁ, d, 3JP-C = 5.0), 120.5
(C-4ꢁꢁ), 125.1 (C-4ꢁꢁꢁ), 127.3 (C-2ꢁ/6ꢁ), 129.2 (C-3ꢁ/5ꢁ), 129.5 (C-3ꢁꢁ/5ꢁꢁ), 129.8 (C-3ꢁꢁꢁ/5ꢁꢁꢁ),
136.0 (C-4ꢁ), 139.7 (C-1ꢁ), 150.8 (C-1ꢁꢁꢁ, d, 2JP-C = 6.9), 151.2 (C-1ꢁꢁ), 153.6 (C-9), 155.4
(C-4, d, 2JP-C = 6.7), 156.7 (C-5), 158.8 (C-2), 161.3 (C-7). 31P NMR: δ –2.63.
Compound 5c. Yellow powder, mp 156–157◦C, yield 32%. HRMS 616.1772 [M
+ H]+ (calculated for C33H31ClN3O5P 615.1690). H NMR: δ 3.05 (t, 4 H, JP-H = 4.9,
H-11/13), 3.49–3.54 (m, 4 H, H-12/14), 3.89 (s, 3 H, 7-OCH3), 3.95 (s, 3 H, 5-OCH3), 6.54
(d, 1 H, 4JH-H = 2.2, H-6), 6.84–6.89 (m, 3 H, H-2ꢁꢁ/4ꢁꢁ/6ꢁꢁ), 7.09 (d, 1 H, 4JH-H = 2.2, H-8),
7.15–7.19 (m, 1 H, H-4ꢁꢁꢁ), 7.22–7.36 (m, 6 H, H-3ꢁꢁꢁ/5ꢁꢁꢁ/3ꢁꢁ/5ꢁꢁ/2ꢁꢁꢁ/6ꢁꢁꢁ), 7.46 (d, 2 H, 3JH-H
1
3
= 2.2, H-3ꢁ/5ꢁ), 7.85 (d, 1 H, JP-H = 1.1, H-3), 8.04 (d, 2 H, JH-H = 6.8, JH-H = 1.7,
4
3
4
H-2ꢁ/6ꢁ). 13C NMR: δ 44.7 (C-12/14), 49.7 (C-11/13, d, 2JP-C = 5.5), 55.6 (7-OCH3), 55.9
3
3
(5-OCH3), 99.6 (C-6), 100.9 (C-8), 106.7 (C-3, d, JP-C = 2.8), 108.5 (C-10, d, JP-C
=
6.9), 116.7 (C-2ꢁꢁ/6ꢁꢁ), 120.1 (C-2ꢁꢁꢁ/6ꢁꢁꢁ, d, 3JP-C = 4.9), 120.6 (C-4ꢁꢁ), 125.2 (C-4ꢁꢁꢁ), 128.7
(C-2ꢁ/6ꢁ), 128.9 (C-3ꢁ/5ꢁ), 129.2 (C-3ꢁꢁ/5ꢁꢁ), 129.8 (C-3ꢁꢁꢁ/5ꢁꢁꢁ), 135.8 (C-4ꢁ), 137.2 (C-1ꢁ),
150.8 (C-1ꢁꢁꢁ, d, 2JP-C = 7.2), 151.2 (C-1ꢁꢁ), 153.6 (C-9), 155.7 (C-4, d, 2JP-C = 6.7), 156.7
(C-5), 157.4 (C-2), 161.5 (C-7). 31P NMR: δ –2.59.
Compound 5d. Yellow powder, mp 153–154◦C, yield 43%. HRMS 610.2471 [M
+ H]+ (calculated for C35H36N3O5P 609.2393). H NMR: δ 2.28 (s, 3 H, 4ꢁ-CH3), 2.42
1
(s, 3 H, 3ꢁꢁ-CH3), 3.02 (t, 4 H, JP-H = 4.8, H-11/13), 3.47–3.52 (m, 4 H, H-12/14), 3.88
3
(s, 3 H, 7-OCH3), 3.95 (s, 3 H, 5-OCH3), 6.52 (d, 1 H, 4JH-H = 2.2, H-6), 6.64–6.70 (m,
3 H, H-2ꢁꢁ/4ꢁꢁ/6ꢁꢁ), 7.11 (d, 1 H, JH-H = 2.3, H-8), 7.12–7.17 (m, 1 H, H-5ꢁꢁ), 7.16–7.18
4
(m, 1 H, H-4ꢁꢁꢁ), 7.26–7.36 (m, 6 H, H-2ꢁꢁꢁ/3ꢁꢁꢁ/5ꢁꢁꢁ/6ꢁꢁꢁ/3ꢁ/5ꢁ), 7.87 (d, 1 H, JP-H = 1.2,
4
H-3), 8.01 (d, 2 H, 3JH-H = 8.2, H-2ꢁ/6ꢁ). 13C NMR: δ 21.3 (4ꢁ-CH3), 21.7 (3ꢁꢁ-CH3), 44.7
(C-12/14), 49.8 (C-11/13, d, 2JP-C = 5.5), 55.6 (7-OCH3), 55.9 (5-OCH3), 99.3 (C-6), 100.9
(C-8), 106.9 (C-3), 108.3 (C-10, d, 3JP-C = 6.7), 117.6 (C-2ꢁꢁ/6ꢁꢁ), 120.2 (C-2ꢁꢁꢁ/6ꢁꢁꢁ, d, 3JP-C
= 5.0), 121.4 (C-4ꢁꢁ), 125.1 (C-4ꢁꢁꢁ), 127.3 (C-2ꢁ/6ꢁ), 129.5 (C-3ꢁ/5ꢁ), 129.0 (C-5ꢁꢁ), 129.8
(C-3ꢁꢁꢁ/5ꢁꢁꢁ), 136.0 (C-3ꢁꢁ), 137.7 (C-1ꢁ), 138.9 (C-4ꢁ), 150.8 (C-1ꢁꢁꢁ, d, 2JP-C = 6.6), 151.3
(C-1ꢁꢁ), 153.6 (C-9), 155.4 (C-4), 156.7 (C-5), 157.7 (C-2), 161.3 (C-7). 31P NMR: δ –2.65.
Compound 5e. Yellow powder, mp 160–161◦C, yield 47%. HRMS 630.1921 [M +
H]+ (calculated for C34H33ClN3O5P 629.1846). 1H NMR: δ 2.41 (s, 3 H, 3ꢁꢁ-CH3), 2.99 (t, 4
H, 3JP-H = 4.8, H-11/13), 3.46–3.51 (m, 4 H, H-12/14), 3.88 (s, 3 H, 7-OCH3), 3.95 (s, 3 H,
5-OCH3), 6.52 (d, 1 H, 4JH-H = 2.3, H-6), 6.73–6.76 (m, 2 H, H-2ꢁꢁ/6ꢁꢁ), 7.11 (d, 1 H, 4JH-H
= 2.3, H-8), 7.15–7.19 (m, 2 H, H-3ꢁ/5ꢁ), 7.26–7.36 (m, 7 H, H-3ꢁꢁ/5ꢁꢁ/2ꢁꢁꢁ/3ꢁꢁꢁ/4ꢁꢁꢁ/5ꢁꢁꢁ/6ꢁꢁꢁ),
7.86 (d, 1 H, JP-H = 1.3, H-3), 7.99 (d, 2 H, JH-H = 1.7, H-2ꢁ/6ꢁ). 13C NMR: δ 21.4
4
3
(4ꢁꢁ-CH3), 44.5 (C-12/14, d, 3JP-C = 2.1), 49.7 (C-11/13, d, 2JP-C = 5.6), 55.6 (7-OCH3),
55.9 (5-OCH3), 99.3 (C-6), 100.9 (C-8), 106.9 (C-3, d, 3JP-C = 3.1), 108.3 (C-10, d, 3JP-C
=

1520
Z. QU ET AL.
6.4), 117.9 (C-2ꢁꢁ/6ꢁꢁ), 120.2 (C-2ꢁꢁꢁ/6ꢁꢁꢁ, d, 3JP-C = 5.0), 125.2 (C-4ꢁꢁ), 125.5 (C-4ꢁꢁꢁ), 127.3
(C-2ꢁ/6ꢁ), 129.1 (C-3ꢁ/5ꢁ), 129.5 (C-3ꢁꢁ/5ꢁꢁ), 129.8 (C-3ꢁꢁꢁ/5ꢁꢁꢁ), 136.0 (C-4ꢁ), 139.8 (C-1ꢁ),
149.8 (C-1ꢁꢁ), 150.8 (C-1ꢁꢁꢁ, d, 2JP-C = 6.7), 153.7 (C-9), 155.4 (C-4, d, 2JP-C = 6.5), 156.6
(C-5), 158.8 (C-2), 161.3 (C-7). 31P NMR: δ –2.76.
Compound 5f. Yellow powder, mp 149–150◦C, yield 32%. HRMS 650.1384 [M
1
3
+ H]+ (calculated for C34H33ClN3O5P 649.1300). H NMR: δ 2.99 (t, 4 H JP-H = 4.8,
H-11/13), 3.47–3.52 (m, 4 H, H-12/14), 3.89 (s, 3 H, 7-OCH3), 3.95 (s, 3 H, 5-OCH3),
6.53 (d, 1 H, JH-H = 2.2, H-6), 6.74–6.77 (m, 2 H, H-2ꢁꢁ/6ꢁꢁ), 7.12 (d, 1 H, JH-H = 2.2,
4
4
H-8), 7.16–7.19 (m, 2 H, H-3ꢁ/5ꢁ), 7.28–7.36 (m, 4 H, H-2ꢁꢁꢁ/3ꢁꢁꢁ/5ꢁꢁꢁ/6ꢁꢁꢁ), 7.43–7.50 (m, 3
H, H-3ꢁꢁ/5ꢁꢁ/4ꢁꢁꢁ), 7.88 (d, 1 H, JP-H = 1.2, H-3), 8.09 (d, 2 H, JH-H = 1.6, H-2ꢁ/6ꢁ). 13C
4
3
2
NMR: δ 44.7 (C-12/14), 49.8 (C-11/13, d, JP-C = 5.5), 55.7 (7-OCH3), 55.9 (5-OCH3),
3
3
99.5 (C-6), 100.9 (C-8), 107.1 (C-3, d, JP-C = 3.0), 108.3 (C-10, d, JP-C = 6.5), 117.9
(C-2ꢁꢁ/6ꢁꢁ), 120.2 (C-2ꢁꢁꢁ/6ꢁꢁꢁ, d, 3JP-C = 5.0), 125.2 (C-4ꢁꢁ), 125.5 (C-4ꢁꢁꢁ), 127.4 (C-2ꢁ/6ꢁ),
128.8 (C-3ꢁ/5ꢁ), 129.0 (C-3ꢁꢁ/5ꢁꢁ), 129.6 (C-4ꢁ), 129.8 (C-3ꢁꢁꢁ/5ꢁꢁꢁ), 138.8 (C-1ꢁ), 149.8 (C-
1ꢁꢁ), 150.7 (C-1ꢁꢁꢁ, d, JP-C = 6.7), 153.6 (C-9), 155.5 (C-4, d, JP-C = 6.7), 156.6 (C-5),
2
2
158.81(C-2), 161.4 (C-7). 31P NMR: δ –2.75.
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