A Very Simple Synthesis of Annelated λ3- and λ5-Phosphanaphthalenes

Article abstract of DOI:10.1002/ejic.201700011

ortho-Phosphinobenzonitriles (or thieno, pyridino analogues) react with dimethyl acetylenedicarboxylate between –78 °C and room temperature to give annelated λ⁵-phosphanaphthalenes. Interesting variations of the fluorescence properties are observed when the R substituents at P are alkyl or aryl. When R = tBu, the thermolysis of the product affords the corresponding trivalent phosphanaphthalene.

Full text of DOI:10.1002/ejic.201700011

A Journal of
Accepted Article
Title: A very simple synthesis of annelated lambda-3 and lambda-5
phosphanaphthalenes
Authors: Francois Mathey, Lujun Zhang, Feichao Yang, Guanyu Tao,
Liqi Qiu, and Zheng Duan
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To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201700011
Link to VoR: http://dx.doi.org/10.1002/ejic.201700011

10.1002/ejic.201700011
European Journal of Inorganic Chemistry
A Very Simple Synthesis of Annelated λ3- and λ5-Phosphanaphthalenes
Lujun Zhang, Feichao Yang, Guanyu Tao, LiqiQiu, Zheng Duan*, François Mathey*
College of Chemistry and Molecular Engineering, International Phosphorus Laboratory, International Joint Research Laboratory for Functional
Organophosphorus Materials of Henan Province, Zhengzhou University, Zhengzhou 450001, P. R. China.
E-mail: duanzheng@zzu.edu.cn; frmathey@yahoo.fr
o
Ortho-phosphino-benzonitriles (or thieno, pyridinoanalogs) react with dimethyl acetylene dicarboxylate between – 78 C and
room temperature to give annelated5-phosphanaphthalenes. Interesting variations of the fluorescence properties are observed
when the R substituents at P are alkyl or aryl. When R = t-Bu, the thermolysis of the product affords the corresponding trivalent
phosphanaphthalene.
Introduction
Phosphorus containing π-conjugated systems are currently receiving special attention, owing to their potential
applications in materials, such as liquid crystals1, organogels2, fibers3, probes4, sensors4, n-type organic semiconductors5,
light-emitting diodes (OLEDs/PLEDs)6 and photovoltaic cells7.Compared with the well-known five-membered arene-
fused phospholes6, the research with the annelated six-membered phosphacycles is restricted by the lack of synthetic
methods. Very recently, Matveeva’s group developed a photochemical heterocyclization of mixed phosphonium–
iodoniumylids with acetylenes to give annelated λ5-phosphinines8. Romero-Nieto's group described a new non-
catalyzed synthetic protocol to prepare phosphaphenalenes9. Here, we would like to report a facile method to
synthesize a new type of functional six-membered phosphanaphthalenes (phosphinolines) from tertiary phosphines
and dimethyl acetylenedicarboxylate (DMAD).
Phosphine catalyzed or mediated Michael addition is a powerful tool in modern organic synthesis10. Nucleophilic
attacks of the phosphorus atom on electron-deficient multiple bonds create reactive zwitterionic carbenoid species,
which emerged as versatile intermediates for various transformations. Some of these reactions provided a direct access
to stable phosphorus-ylids containing conjugated heterocycles11. This led us to investigate the intramolecular
nucleophilic reactivity between this type of zwitterionic carbenoid species and the cyanide group.
Results and discussion
After optimization of the reaction conditions (temperature, solvent), 2-diphenylphosphinobenzonitrile1a was reacted
o
with DMAD at -78 C in anhydrous toluene for 30 min (Scheme 1). Then, the reaction mixture was stirred at r.t. and
monitored by 31P NMR spectroscopy. The reaction was quite clean and a new product was isolated with a 31P resonance
at 13.2 ppm. Its structure was established by crystallographic analysis. It appeared that this reaction provides a facile
access to annelated six-membered phosphacycle2a from readily accessible starting materials. Various α-phosphino
benzonitriles reacted smoothly with DMAD to give the annelated phosphacycles. Both aryl-, alkyl- and even amino-
substituted phosphines could be used (2a
gavehigher yields (2e ) than those with electron withdrawing groups, such as CN (2g), F (2h) and Cl (2i). Hetero-arene
fused phosphacyclescould also be obtained using this new method (2j ). It is interesting to note that all the solutions
of alkyl-substituted phosphacycles (2c 2d, and 2k) could be excited by UV light and yields yellow emission, whereas this
-2d, 2l). α-Phosphinobenzonitriles substituted by electron donating groups
-
f
-
k
,
phenomenon was not observed with all the aryl-substituted derivatives (Figure 1).
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10.1002/ejic.201700011
European Journal of Inorganic Chemistry
Scheme 1 Reactions of α-phosphinobenzonitriles with DMAD
Figure 1UV-vis absorption and fluorescence spectra (inset) of 2a, 2c, 2d and 2e in CH2Cl2(10-5 M) at r.t.Photographs of 2a, 2c, 2d and 2e under irradiation with black
light at 365 nm areshown in the inset.
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10.1002/ejic.201700011
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Crystallographic studies were carried out on 2a and 2c (Figures 2 and 3). The intracyclic C(5)-P(1) bond lengths are
1.753(3) Å (2a) and 1.763(2) Å (2c), respectively, which are consistent with their ylidic structure12. The phosphorus ring
of 2c is nearly planar (
∠C5-P1-C9-C14 = 3.07°) whereas the ring of 2a is significantly distorted (∠C5-P1-C9-C14 = 26.31°).
This suggests a higher electronic delocalization within the phosphorus ring of 2c when compared to 2a
.
Figure 2 ORTEP drawing of 2a (50% thermal ellipsoids). Main distances (Å) and angles (deg.): P1-C5 1.753(3), P1-C4 1.796(3), P1-C9 1.803(3), P1-C18 1.823(3), C5-C6
1.425(4), C6-C15 1.372(4), C14-C15 1.450(4), C9-C14 1.417(4); C4-P1-C9 109.34(14), C4-P1-C18 107.50(13),C5-P1-C4 113.67(14), C5-P1-C9 107.58(13), C5-P1-C18
112.30(13), C9-P1-C18 106.17(13); C5-P1-C9-C14 = 26.31°.
Figure 3 ORTEP drawing of 2c(50% thermal ellipsoids). Main distances (Å) and angles (deg.): P1-C5 1.762(2), P1-C4 1.8273(19), P1-C9 1.806(2), P1-C18 1.837(2), C5-
C6 1.421(3), C6-C15 1.356(3), C14-C15 1.433(3), C9-C14 1.414(3); C4-P1-C9 105.65(9), C4-P1-C18 108.50(10), C5-P1-C4 115.34(9), C5-P1-C9 106.52(10), C5-P1-C18
111.66(10), C9-P1-C18 108.83(9); C5-P1-C9-C14 = 3.07°.
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10.1002/ejic.201700011
European Journal of Inorganic Chemistry
Scheme 2 Synthesis of annelatedphosphinined
From a purely synthetic standpoint, this method appears to be quite general. Indeed it is possible to extend its use
to the synthesis of annelatedphosphinines (Scheme 2).
In another vein, when the substituents at phosphorus are t-Bu (2d), it is possible to convert a λ5- into a λ3-
phosphanaphthalene by thermolysis (Scheme 3).
Scheme 3 Synthesis of a λ3-phosphanaphthalene
The phosphanaphthalene
6
has been detected by 31P MNR (31P 190 ppm), but, due to its high reactivity, we trapped
it by reaction with 2,3-dimethylbutadiene and sulfur (compound
characterized by X-ray crystal structure analysis (Figure 4).
7) as shown in Scheme 3. Compound 7 has been
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10.1002/ejic.201700011
European Journal of Inorganic Chemistry
Figure 4 ORTEP drawing of 7 (30% thermal ellipsoids). Main distances (Å) and angles (deg.): P1-C1 1.811(2), P1-C11 1.852(2), P1-C15 1.814(3), P1-S1 1.9421(9), C1-
C6 1.411(3), C6-C7 1.466(3), C7-C8 1.340(3), C8-C11 1.496(3); C1-P1-C11 105.13(11), C1-P1-C15 104.44(12), C1-P1-S1 113.85(8), C11-P1-S1 114.96(8), C15-P1-C11
100.73(11), C15-P1-S1 116.17(10).
Scheme 4 Proposed mechanism
On the basis of the known reaction of phosphines and DMAD, we propose the following mechanism (Scheme 4)
involving a sequence of nucleophilic addition of phosphines 1 to DMAD to form zwitterionic intermediates, followed by
an intramolecular cascade nucleophilic attack of CN- on the carbonyl groups.
Conclusion
In conclusion, we have developed a very simple one-step synthesis of annelated λ5-phosphanaphthalenes whose
fluorescence properties vary with the substitution at phosphorus. Further studies will describe more in depth the
optoelectronic properties of this new class of conjugated materials. The same scheme can also afford annelated
phosphinines and trivalent phosphanaphthalenes.
Experimental section
All reactions were performed under nitrogen using solvents dried by standard methods. 1H, 13C and 31P NMR spectra were
recorded on Bruker 300 and 400 MHz spectrometer. Chemical shifts are expressed in ppm from internal TMS (1H and13C). All
coupling constants (J values) are reported in hertz (Hz). HRMS spectra were obtained on a Water Q‐Tof Premier MS. Element
analytic data were obtained on a Thermo Electron Corporation flash EA 1112 element spectrometer. Silica gel (230‐400 mesh)
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10.1002/ejic.201700011
European Journal of Inorganic Chemistry
was used for the chromatographic separations. The UV-VIS spectra were recorded on a Varian Cary 5000 UV-Vis-NIR
Spectrophotometer at room temperature. The emission spectra were recorded on a HITACHI F-4600 Fluorescence
Spectrophotometer at room temperature. 2a: λabsmax= 351 nm (ε = 7916 mol-1 L cm-1 ), 2c: λabsmax = 368 nm (ε = 7835 mol-1 L cm-
1 ), 2d: λabsmax = 366 nm (ε = 6009 mol-1 L cm-1), 2e: λabsmax = 342 nm (ε = 10865 mol-1 L cm-1). 1g, 1j, 1m and 1n were prepared
according to literature methods. Ph(Et2N)PCl was made by the reaction of PhPCl2 with HNEt2 in anhydrous Et2O. Commercially
available reagents were used without further purification.
Synthesis of the starting phosphines
Procedure A for the Synthesis of Compounds 1a-1b, 1e-1f, 1h-1j:
To a solution of ortho-bromoaryl nitriles or 2-bromothiophen-3-carbonitrile (15 mmol) in anhydrous THF (60 mL) (for 1a, 1b , 1e
and 1f) or Et2O (60 mL) (for 1j) or THF/Et2O (30 /30 mL) (for 1h and 1i), kept in an oven-dried 100 mL-Schlenk flask under an
atmosphere of dry nitrogen, was added dropwise a 1.6 M solution of n-BuLi in hexane (9.4 mL, 15 mmol) at –78 °C over a period
of 5 min. After stirring at –78 oC for 1 h, Ar2PCl (15 mmol) in anhydrous THF (10 mL) was added dropwise. The mixture was kept
o
at –78 C for 1 h and then warmed to room temperature. After 1h, the reaction was monitored by 31P NMR spectroscopy. The
mixture was diluted with diethyl ether, the organic phase washed with water, brine and dried over anhydrous MgSO4. The
solvents were removed under reduced pressure to give a crude product, which was purified by column chromatography on silica
gel (petroleum ether/ dichloromethane).
Procedure B for the Synthesis of Compound 1g:
To a solution of 1,3-dicyanobenzene (2.56 g, 20 mmol) in anhydrous THF (50 mL), kept in an oven-dried 100 mL-Schlenk flask
under an atmosphere of dry nitrogen, was added dropwise LDA (22 mmol) (which was prepared by the reaction of n-BuLi and
HN(i-Pr)2) in THF at –78 oC over a period of 10 min. After stirring at –78 oC for 1 h, Ph2PCl (4.42 g, 20 mmol) in anhydrous THF (10
mL) was added dropwise. The mixture was kept at –78 oC for 1 h and then warmed to room temperature. After 1h, the reaction
was monitored by 31P NMR spectroscopy. The mixture was diluted with diethyl ether, the organic phase washed with water, brine
and dried over anhydrous MgSO4. The solvents were removed under reduced pressure to give a crude product, which was purified
by column chromatography on silica gel (petroleum ether/ dichloromethane).
Procedure C for the Synthesis of Compounds 1c(O)-1d(O), 1k(O)-1l(O):
To a solution of 2-bromobenzonitrile or 2-bromopyridine-3-carbonitrile (9.6 mmol) in anhydrous THF (40 mL) (for 1c, 1d, and 1l)
or THF/Et2O (20/20 mL) (for 1k), kept in an oven-dried 100 mL-Schlenk flask under an atmosphere of dry nitrogen, was added
dropwise a 1.6 M solution of n-BuLi in hexane (6.0 mL, 9.6 mmol) at –78 oC over a period of 5 min. After stirring at –78 oC for 1 h,
o
RR’PCl (9.6 mmol) in anhydrous THF (10 mL) was added dropwise. The mixture was kept at –78 C for 1 h and then warmed to
room temperature. After 3 h, the reaction was monitored by 31P NMR spectroscopy. The solvents were removed under reduced
pressure and dichloromethane was added to the reaction mixture. After the residue was dissolved, the mixture was filtered to
remove salt. H2O2 (ca. 30 %, a few drops) was added to the filtrate while stirring. After 10 min, the mixture was diluted with
dichloromethane, the organic phase washed with water, brine and dried over anhydrous MgSO4. The solvents were removed
under reduced pressure to give a crude product, which was purified by column chromatography on silica gel (petroleum ether/
diethyl ether).
Procedure D for the Synthesis of the Compound 1m(O):
To a solution of 1-bromocyclohexene-2-carbonitrile (1190 mg, 6.4 mmol) in anhydrous THF/Et2O (20/20 mL), kept in an oven-
dried 100 mL-Schlenk flask under an atmosphere of dry nitrogen, was added dropwise a 1.6 M solution of n-BuLi in hexane (4.0
mL, 6.4 mmol) at –78 oC over a period of 5 min. After stirring at –78 oC for 1 h, Ph2PCl (1412 mg, 6.4 mmol) in anhydrous THF (10
mL) was added dropwise. The mixture was kept at –78 oC for 1 h and then warmed to room temperature. After 3 h, the reaction
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10.1002/ejic.201700011
European Journal of Inorganic Chemistry
was monitored by 31P NMR spectroscopy. The solvents were removed under reduced pressure and dichloromethane was added
to the reaction mixture. After the residue was dissolved, the mixture was filtered to remove salt. H2O2 (ca. 30 %, a few drops) was
added to the filtrate while stirring. After 10 min, the mixture was diluted with dichloromethane, the organic phase washed with
water, brine and dried over anhydrous MgSO4. The solvents were removed under reduced pressure to give a crude product, which
was purified by column chromatography on silica gel (petroleum ether/ diethyl ether).
Phosphine 1a
White solid, 3.28 g, 76 % yield. 31P NMR (121 MHz, CDCl3): δ -8.3 ppm; 1H NMR (300 MHz, CDCl3): δ 7.06-7.10 (m, 1H), 7.27-7.51
(m, 12H), 7.70-7.74 (m, 1H); 13C NMR (75 MHz, CDCl3): δ 117.66 (d, JCP = 3.8 Hz, CN), 117.93 (d, JCP = 33.0 Hz, C), 128.88 (d, JCP
=
7.5 Hz, 4CH), 128.93 (s, CH), 129.48 (s, 2CH), 132.47 (s, CH), 133.45 (s, CH), 133.76 (d, JCP = 4.5 Hz, CH), 134.05 (d, JCP = 20.3 Hz,
4CH), 134.70 (d, JCP = 10.5 Hz, 2C), 143.03 (d, JCP = 20.3 Hz, C). HRMS: m/z calcd. for C19H15NP [M+H]+: 288.0942; found : 288.0945.
Phosphine 1b
White solid, 2.93 g, 62 % yield. 31P NMR (121 MHz, CDCl3): δ -10.7 ppm; 1H NMR (300 MHz, CDCl3): δ 2.38 (s, 6H, 2Me), 7.04-7.08
(m, 1H), 7.19-7.27 (m, 8H), 7.37-7.50 (m, 2H), 7.68-7.72 (m, 1H); 13C NMR (75 MHz, CDCl3): δ 21.42 (s, 2CH3), 117.62 (d, JCP = 32.3
Hz, C), 117.74(d, JCP = 3.8 Hz, CN), 128.64 (s, CH), 129.67 (d, JCP = 7.5 Hz, 4CH), 131.27 (d, JCP = 8.3 Hz, 2C), 132.34 (s, CH), 133.20
(s, CH), 133.69 (d, JCP = 4.5 Hz, CH), 134.07 (d, JCP = 21.0 Hz, 4CH), 139.50 (s, 2C), 143.82 (d, JCP = 19.5 Hz, C). HRMS: m/z calcd for
C21H19NP [M+H]+: 316.1255; found : 316.1259.
Phosphine oxide1c(O)
White solid, 2.39 g, 79% yield. 31P NMR (121 MHz, CDCl3): δ 46.4 ppm; 1H NMR (300 MHz, CDCl3): δ 1.08-1.52 (m, 12H), 1.64-1.84
(m, 6H), 2.07-2.11 (m, 2H), 2.34-2.44 (m, 2H), 7.60 (t, J = 7.8 Hz, 1H), 7.71-7.79 (m, 2H), 8.16-8.22 (m, 1H); 13C NMR (75 MHz,
CDCl3): δ 25.48 (d, JCP = 3.8 Hz, 2CH2), 25.65 (d, JCP = 0.8 Hz, 2CH2), 25.98 (d, JCP = 3.8 Hz, 2CH2), 26.07 (s, CH2), 26.22 (d, JCP = 3.0
Hz, 2CH2), 26.38 (s, CH2), 36.19 (d, JCP = 66.0 Hz, 2CH), 112.74 (d, JCP = 6.0 Hz, C), 118.72 (d, JCP = 3.0 Hz, CN), 131.30 (d, JCP = 2.3 Hz,
CH), 132.64 (d, JCP = 9.0 Hz, CH), 134.24 (d, JCP = 6.8 Hz, CH), 135.39 (d, JCP = 72.8 Hz, C), 135.52 (d, JCP = 4.5 Hz, CH). HRMS: m/z
calcd for C19H27NOP [M+H]+: 316.1830; found : 316.1829.
Phosphine oxide 1d(O)
31P NMR (121 MHz, CDCl3): δ 53.7 ppm. HRMS: m/z calcd for C15H23NOP [M+H]+: 264.1517; found : 264.1516.
Phosphine 1e
White solid, 2.53 g, 53 % yield. 31P NMR (121 MHz, CDCl3): δ-7.9 ppm; 1H NMR (300 MHz, CDCl3): δ 3.69 (s, 3H, MeO), 6.52 (t, J =
3.0 Hz, 1H), 6.90 (dd, J = 2.4, 8.4 Hz, 1H), 7.27-7.41 (m, 10H), 7.66 (dd, J = 3.3, 8.7 Hz, 1H); 13C NMR (75 MHz, CDCl3): δ 55.4 (s,
CH3O), 109.3 (d, JCP = 31.5 Hz, C), 113.9 (s, CH), 118.03 (d, JCP = 3.8 Hz, CN), 119.7 (s, CH), 128.9 (d, JCP = 7.5 Hz, 4CH), 129.5 (s,
2CH), 134.1 (d, JCP = 20.3 Hz, 4CH), 134.5 (d, JCP = 10.5 Hz, 2C), 135.6 (d, JCP = 5.3 Hz, CH), 145.2 (d, JCP = 20.3 Hz, C), 162.4 (s. C).
HRMS: m/z calcd for C20H17NOP [M+H]+: 318.1048; found : 318.1049.
Phosphine 1f
White solid, 3.96 g, 88 % yield. 31P NMR (121 MHz, CDCl3): δ-9.9 ppm; 1H NMR (300 MHz, CDCl3): δ 2.39 (s, 3H, Me), 6.97 (d, J =
7.8 Hz, 1H), 7.27-7.39 (m, 11H), 7.54 (s, H); 13C NMR (75 MHz, CDCl3): δ 20.97 (s, CH3), 117.87 (d, JCP = 4.5 Hz, CN), 117.96 (d, JCP
=
33.8 Hz, C), 128.80 (d, JCP = 7.5 Hz, 4CH), 129.32 (s, 2CH), 133.50 (s, CH), 133.62 (s, CH), 133.91 (d, JCP = 20.3 Hz, 4CH), 134.21 (d,
JCP = 4.5 Hz, CH), 135.07 (d, JCP = 10.5 Hz, 2C), 139.25 (d, JCP = 18.0 Hz, C), 139.48 (s. C). HRMS: m/z calcd for C20H17NP [M+H]+:
302.1099; found : 302.1101.
Phosphine 1g
White solid, 4.50 g, 72% yield. 31P NMR (121 MHz, CDCl3): δ -2.4 ppm; 1H NMR (300 MHz, CDCl3): δ 7.43-7.53 (m, 10H), 7.60 (t, J
= 7.8 Hz, 1H), 7.91 (dd, J = 1.2, 7.8 Hz, 2H); 13C NMR (75 MHz, CDCl3): δ 116.14 (d, JCP = 2.3 Hz, 2CN), 120.58 (d, JCP = 19.5 Hz, 2C),
129.10 (d, JCP = 6.8 Hz, 4CH), 130.01 (s, 2CH), 130.18 (s, CH), 132.25 (d, JCP = 9.8 Hz, 2C), 133.62 (d, JCP = 20.3 Hz, 4CH), 138.50 (d,
JCP = 2.3 Hz, 2CH), 145.73 (d, JCP = 35.3 Hz, C). HRMS: m/z calcd for C20H14N2P [M+H]+: 313.0895; found : 313.0891.
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10.1002/ejic.201700011
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Phosphine 1h
White solid, 2.25 g, 49 % yield. 31P NMR (121 MHz, CDCl3): δ -9.6 ppm; 1H NMR (300 MHz, CDCl3): δ 6.70-6.75 (m, 1H), 7.07-7.14
(m, 1H), 7.31-7.44 (m, 10H), 7.70-7.75 (m, 1H); 13C NMR (75 MHz, CDCl3): δ 113.64 (dd, J = 3.0, 30.8 Hz, C), 116.49 (d, J= 22.5 Hz,
CH), 116.92 (d, J = 3.0 Hz, CN), 120.57 (d, J= 22.5 Hz, CH), 129.08 (d, J= 7.5 Hz, 4CH), 129.86 (s, 2CH), 133.83 (d, J= 9.8 Hz, 2C),
134.12 (d, J= 20.3 Hz, 4CH), 136.15 (dd, J = 4.5, 9.0 Hz, CH), 147.58 (dd, J = 6.0, 23.3 Hz, C), 164.71 (d, J= 257.3 Hz, C). HRMS: m/z
calcd for C19H14FNP [M+H]+: 306.0848; found : 306.0845.
Phosphine 1i
White solid, 2.70 g, 56 % yield. 31P NMR (121 MHz, CDCl3): δ-9.4 ppm; 1H NMR (300 MHz, CDCl3): δ 7.02 (dd, J = 2.7, 8.4 Hz, 1H),
7.27-7.48 (m, 11H), 7.70 (s, 1H); 13C NMR (75 MHz, CDCl3): δ 116.39 (d, JCP = 3.0 Hz, CN), 119.26 (d, JCP = 34.5 Hz, C), 129.03 (d, JCP
= 7.5 Hz, 4CH), 129.72 (s, 2CH), 132.82 (s, CH), 133.30 (d, JCP = 4.5 Hz, CH), 134.02 (d, JCP = 20.3 Hz, 4CH), 134.15 (s, C), 134.73 (d,
JCP = 67.5 Hz, 2C), 134.79 (s, CH), 141.85 (d, JCP = 21.8 Hz, C). HRMS: m/z calcd for C19H14ClNP [M+H]+: 322.0552; found : 322.0554.
Phosphine 1j
1
Yellow solid, 3.39 g, 77% yield. 31P NMR (121 MHz, CDCl3): δ -20.9 ppm; H NMR (300 MHz, CDCl3): δ 7.36-7.43 (m, 11H), 7.55-
7.57 (m, 1H); 13C NMR (75 MHz, CDCl3): δ 114. 69 (d, JCP = 1.5 Hz, CN), 117.46 (d, JCP = 27.8 Hz, C), 128.84 (d, JCP = 7.5 Hz, 4CH),
129.77 (s, 2CH), 130.88 (d, JCP = 3.0 Hz, CH), 131.97 (s, CH), 133.35 (d, JCP = 20.3 Hz, 4CH), 135.25 (d, JCP = 9.0 Hz, 2C), 151.57 (d, JCP
= 39.8 Hz, C). HRMS: m/z calcd for C17H13NPS [M+H]+: 294.0506; found : 294.0511.
Phosphine oxide1k(O)
White solid, 2.43 g, 80% yield. 31P NMR (121 MHz, CDCl3): δ 51.1 ppm; 1H NMR (300 MHz, CDCl3): δ 1.10-1.47 (m, 14H), 1.64-1.73
(m, 3H), 1.81-1.83 (m, 1H), 2.12-2.16 (m, 2H), 2.28-2.40 (m, 2H), 7.54-7.59 (m, 1H), 8.12-8.16 (m, 1H), 8.89-8.91 (m, 1H);13C NMR
(75 MHz, CDCl3): δ 24.59 (d, JCP = 3.0 Hz, 2CH2), 25.27 (d, JCP = 3.8 Hz, 2CH2), 25.65 (s, 2CH2), 26.10 (s, 2CH2), 26.27 (s, 2CH2), 35.32
(d, JCP = 66.0 Hz, 2CH), 115.66 (s, CN), 115.85 (d, JCP = 12.0 Hz, C), 124.52 (d, JCP = 3.0 Hz, CH), 142.21 (d, JCP = 5.3 Hz, CH), 151.67
(d, JCP = 15.8 Hz, CH), 157.91 (d, JCP = 102.8 Hz, C). HRMS: m/z calcd for C18H26N2OP [M+H]+: 317.1816; found : 317.1815.
Phosphine oxide1l(O)
White solid, 2.4 g, 84% yield. 31P NMR (121 MHz, CDCl3): δ 26.2 ppm; 1H NMR (300 MHz, CDCl3): δ 1.07 (t, J = 6.9 Hz, 6H), 3.02-
3.12 (m, 4H), 7.32-7.59 (m, 5H), 7.67-7.71 (m, 1H), 7.85-7.93 (m, 2H), 8.06-8.13 (m, 1H); 13C NMR (75 MHz, CDCl3): δ 13.60 (d, JCP
= 3.8 Hz, 2CH3), 39.49 (d, JCP = 3.0 Hz, 2CH2), 114.37 (d, JCP = 4.5 Hz, C), 118.23 (d, JCP = 4.5 Hz, CN), 128.59 (d, JCP = 12.8 Hz, 2CH),
130.84 (d, JCP = 130.5 Hz, C), 131.66 (d, JCP = 2.3 Hz, CH), 132.19 (d, JCP = 2.3 Hz, CH), 132.20 (d, JCP = 9.8 Hz, 2CH),132.52(d, JCP
=
11.3 Hz, CH), 135.15 (d, JCP = 8.3 Hz, CH), 135.68 (d, JCP = 8.3 Hz, CH), 136.59 (d, JCP = 122.3 Hz, C). HRMS: m/z calcd for C17H20N2OP
[M+H]+: 299.1313; found : 299.1313.
Phosphine oxide1m(O)
White solid, 1.57 g, 80 % yield. 31P NMR (121 MHz, CDCl3): δ 27.0 ppm; 1H NMR (300 MHz, CDCl3): δ 1.63-1.65 (m, 4H), 2.28-2.31
(m, 2H), 2.41-2.43 (m, 2H), 7.44-7.58 (m, 6H), 7.67-7.74 (m, 4H); 13C NMR (75 MHz, CDCl3): δ 20.93 (s, CH2), 21.08 (d, JCP = 7.5 Hz,
CH2), 27.99 (d, JCP = 7.5 Hz, CH2), 31.14 (d, JCP = 9.0 Hz, CH2), 116.58 (d, JCP = 10.5 Hz, CN), 122.75 (s, C), 128.79 (d, JCP = 12.8 Hz,
4CH), 130.35 (d, JCP = 104.3 Hz, 2C), 131.94 (d, JCP = 9.8 Hz, 4CH), 132.65 (d, JCP = 3.0 Hz, 2CH), 148.91 (d, JCP = 87.0 Hz, C). HRMS:
m/z calcd for C19H19NOP [M+H]+: 308.1204; found : 308.1202.
Procedure E for the Synthesis of Compounds 2a-2b, 2e-2f, 2g-2j:
To a solution of phosphines (1a-1b, 1e-1f, 1g-1j) (1 mmol) in anhydrous toluene (20 mL) was added DMAD (136 l, 1.1 mmol) at
–78 oC under N2 atmosphere. The mixture was kept at –78 oC for 30 min and then warmed to room temperature. After 2h, the
31P NMR spectrum showed that the reaction was completed. The solvents were removed under reduced pressure to give a crude
product, which was purified by column chromatography on silica gel (dichloromethane/ diethyl ether).
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10.1002/ejic.201700011
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Procedure F for the Synthesis of Compounds 2c-2d, 2k-2l:
To a solution of 2-bromobenzonitrile or 2-bromopyridine-3-carbonitrile (3.2 mmol) in anhydrous THF (30 mL) (for 2c, 2d, and 2l)
or THF/Et2O (15/15 mL) (for 2k), kept in an oven-dried 50 mL-Schlenk flask under an atmosphere of dry nitrogen, was added
dropwise a 1.6 M solution of n-BuLi in hexane (2.0 mL, 3.2 mmol) at –78 oC over a period of 5 min. After stirring at –78 oC for 1 h,
RR’ PCl (3.2 mmol, except for t-Bu2PCl 1.6 mmol) was added dropwise. The mixture was kept at –78 oC for 1 h and then warmed
to room temperature. After 3 h, the 31P NMR spectrum showed that the reaction was completed. The solvents were removed
under reduced pressure and toluene was added to the reaction mixture. After the residue was dissolved, the mixture was filtered
under an atmosphere of dry nitrogen to remove the inorganic salt. At –78 oC DMAD (431 l, 3.5 mmol) was added to the filtrate
while stirring. After 30 min, the mixture was warmed to room temperature. After 2 h, the reaction was complete according to
the 31P NMR spectrum. Then the solvents were removed under reduced pressure to give a crude product, which was purified by
column chromatography on silica gel (dichloromethane / diethyl ether).
Procedure G for the Synthesis of the Compound 2m:
To a solution of 1-bromocyclohexene-2-carbonitrile (1190 mg, 6.4 mmol) in anhydrous THF/Et2O (20/20 mL), kept in an oven-
dried 100 mL-Schlenk flask under an atmosphere of dry nitrogen, was added dropwise a 1.6 M solution of n-BuLi in hexane (4.0
mL, 6.4 mmol) at –78 oC over a period of 5 min. After stirring at –78 oC for 1 h, Ph2PCl (1412 mg, 6.4 mmol) was added dropwise.
The mixture was kept at –78 oC for 1 h and then warmed to room temperature. After 3 h, the 31P NMR spectrum showed that the
reaction was completed. The solvents were removed under reduced pressure and toluene was added to the reaction mixture.
o
After the residue was dissolved, DMAD (788 l, 6.4 mmol) was added to the mixture at –78 C while stirring. After 30 min, the
mixture was warmed to room temperature. After 2 h, the reaction was complete according to the 31P NMR spectrum. Then the
solvents were removed under reduced pressure to give a crude product, which was purified by column chromatography on silica
gel (dichloromethane / diethyl ether).
Procedure H for the Synthesis of the Compound 2n:
To a solution of phosphine 1a (288 mg, 1 mmol) in anhydrous toluene (20 mL) was added the alkyne (121 mg, 1.1 mmol) at –78
o
oC under N2 atmosphere. The mixture was kept at –78 C for 30 min and then warmed to room temperature. After 2h, the 31P
NMR spectrum showed that the reaction was complete. The solvents were removed under reduced pressure to give a crude
product, which was purified by column chromatography on silica gel (dichloromethane/ diethyl ether).
Phosphanaphthalene2a
Yellow solid, 200 mg, 47 % yield. 31P NMR (121 MHz, CDCl3): δ 13.2 ppm; 1H NMR (300 MHz, CDCl3): δ 3.61 (br s, 3H, OMe), 4.12
(s, 3H, OMe), 6.98-7.03 (m, 1H), 7.24-7.31 (m, 1H), 7.45-7.56 (m, 7H), 7.68-7.84 (m, 5H); 13C NMR (75 MHz, CDCl3): δ 45.54 (d, JCP
= 119.3 Hz, P=C), 50.45 (s, CH3, OMe), 57.84 (s, CH3, OMe), 108.28 (d, JCP = 88.5 Hz, C), 116.24 (d, JCP = 7.5 Hz, C), 121.32 (d, JCP
8.3 Hz, CH), 123.03 (d, JCP = 12.8 Hz, CH), 127.38 (d, JCP = 92.3 Hz, 2C), 128.63 (d, JCP = 12.8 Hz, 4CH), 131.96 (d, JCP = 3.0 Hz, 2CH),
132.22 (d, JCP = 2.3 Hz, CH), 132.68 (d, JCP = 8.3 Hz, CH), 133.13 (d, JCP = 11.3 Hz, 4CH), 136.35 (d, JCP = 6.0 Hz, C), 145.73 (d, JCP
=
=
23.3 Hz, C), 159.25 (s, C), 166.01 (b, CO2). HRMS calcd for C25H21NO4P [M+H]+: 430.1203; found : 430.1196. Anal. Calcd for
C25H20NO4P: C 69.93, H 4.69, N 3.26; found: C 69.78, H 4.63, N 3.15.
Phosphanaphthalene2b
Yellow solid, 244 mg, 53 % yield. 31P NMR (121 MHz, CDCl3): δ 12.7 ppm; 1H NMR (300 MHz, CDCl3): δ 2.38 (s, 6H, 2Me), 3.60 (br
s, 3H, OMe), 4.10 (s, 3H, OMe), 6.95-7.00 (m, 1H), 7.23-7.29 (m, 5H), 7.44 (m, 1H), 7.59 (dd, J = 8.4, 13.2 Hz, 4H), 7.79 (dd, J = 4.5,
7.8 Hz, 1H); 13C NMR (75 MHz, CDCl3): δ 21.55 (d, JCP = 0.8 Hz, 2CH3), 45.91 (d, JCP = 120.8 Hz, P=C), 50.40 (br s, CH3, OMe), 57.78
(s, CH3, OMe), 109.00 (d, JCP = 91.5 Hz, C), 116.13 (s, C), 121.19 (d, JCP = 7.5 Hz, CH), 122.92 (d, JCP = 12.8 Hz, CH), 124.25 (d, JCP
=
96.0 Hz, 2C), 129.40 (d, JCP = 13.5 Hz, 4CH), 132.06 (s, CH), 132.65 (d, JCP = 8.3 Hz, CH), 133.15 (d, JCP = 11.3 Hz, 4CH), 136.26 (d, JCP
= 6.0 Hz, 2C), 142.57 (d, JCP = 3.0 Hz, C), 145.88 (d, JCP = 24.8 Hz, C), 159.19 (s, C), 165.89 (b, CO2). HRMS calcd for C27H25NO4P
[M+H]+: 458.1516; found : 458.1509.
Phosphanaphthalene2c
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10.1002/ejic.201700011
European Journal of Inorganic Chemistry
Yellow solid, 470 mg, 33 % yield. 31P NMR (121 MHz, CDCl3): δ 27.2 ppm; 1H NMR (300 MHz, CDCl3): δ 1.13-1.54 (m, 10H), 1.66-
1.77 (m, 8H), 2.03 (m, 2H), 2.83 (d, J = 11.1 Hz, 2H), 3.74 (s, CH3, OMe), 4.06 (s, CH3, OMe), 7.02 (m, 1H), 7.45-7.53 (m, 2H), 7.67
(m, 1H);13C NMR (75 MHz, CDCl3): δ 25.81 (s, 2CH2), 26.67 (d, JCP = 3.0 Hz, 2CH2), 26.85 (d, JCP = 3.0 Hz, 2CH2), 27.04 (d, JCP = 3.0
Hz, 2CH2), 27.54 (d, JCP =2.3 Hz, 2CH2), 36.1 (d, JCP =51.0 Hz, 2CH), 41.19 (d, JCP =108.8 Hz, P=C), 50.43 (s, CH3, OMe), 57.62 (s, CH3,
OMe), 106.80 (d, JCP = 76.5 Hz, C), 115.14 (d, JCP = 3.8 Hz, C), 121.27 (d, JCP = 6.8 Hz, CH), 122.14 (d, JCP = 11.3 Hz, CH), 130.90 (d, JCP
= 8.3 Hz, CH), 132.14 (s, CH), 138.23 (s, C), 146.76 (d, JCP = 18.0 Hz, C), 158.70 (s, C), 166.82 (b, CO2). HRMS calcd for C25H33NO4P
[M+H]+: 442.2142; found : 442.2125. Anal. Calcd for C25H32NO4P: C 68.01, H 7.31, N 3.17; found: C 67.85, H 7.32, N 3.10.
Phosphanaphthalene2d
Yellow solid, 374 mg, 30 % yield. 31P NMR (121 MHz, CDCl3): δ 40.1 ppm; 1H NMR (300 MHz, CDCl3): δ 1.45 (d, J = 15.6 Hz, 18H,
6CH3), 3.75 (s, 3H, OMe), 4.07 (s, 3H, OMe), 6.96 (t, J = 6.9 Hz, 1H), 7.40-7.45 (m, 1H), 7.71-7.77 (m, 2H); 13C NMR (75 MHz, CDCl3):
δ 29.36 (d, JCP = 2.3 Hz, 6 CH3), 42.96 (d, JCP = 40.5 Hz, 2C), 46.32 (d, JCP = 102.8 Hz, P=C), 50.53 (s, CH3, OMe), 57.57 (s, CH3, OMe),
107.76 (d, JCP = 70.5 Hz, C), 115.14 (s, C), 120.58 (d, JCP = 11.3 Hz, CH), 121.59 (d, JCP = 6.8 Hz, CH), 131.79 (s, CH), 134.09 (d, JCP
=
7.5 Hz, CH), 138.17 (s, C), 147.43 (d, JCP = 18.0 Hz, C), 158.64 (s, C), 167.67 (d, JCP = 14.3 Hz, CO2). HRMS calcd for C21H29NO4P
[M+H]+: 390.1829; found : 390.1809. Anal. Calcd for C21H28NO4P: C 64.77, H 7.25, N 3.60; found: C 64.89, H 7.45, N 3.33.
Phosphanaphthalene2e
Red solid, 265 mg, 58 % yield. 31P NMR (121 MHz, CDCl3): δ 13.5 ppm; 1H NMR (300 MHz, CDCl3): δ 3.61 (br s, 3 H, OMe), 3.68 (s,
3H, Ph-OMe), 4.11 (s, 3H, OMe), 6.75 (dd, J = 2.7, 13.8 Hz, 1H), 7.12 (d, J = 9.0 Hz, 1H), 7.38-7.61 (m, 6H), 7.69-7.76 (m, 5H);13C
NMR (101 MHz, CDCl3): δ 44.46 (d, JCP = 122.2 Hz, P=C), 50.37 (s, CH3, OMe), 55.48 (s, CH3, Ph-OMe), 57.75 (s, CH3, OMe), 109.50
(d, JCP = 88.9 Hz, C), 116.26 (s, C), 116.81 (d, JCP = 9.1 Hz, CH), 119.35 (s, CH), 123.12 (d, JCP = 9.1 Hz, CH), 127.24 (d, JCP = 93.9 Hz,
2C), 128.62 (d, JCP = 12.1 Hz, 4CH), 130.42 (s, C), 131.95 (d, JCP = 2.0 Hz, 2CH), 133.10 (d, JCP = 11.1 Hz, 4CH), 143.79 (d, JCP = 24.2
Hz, C), 155.59 (d, JCP = 14.1 Hz, C), 159.22 (s, C), 166.00 (b, CO2). HRMS calcd for C26H23NO5P [M+H]+: 460.1308; found : 460.1297.
Anal. Calcd for C26H22NO5P: C 67.97, H 4.83, N 3.05; found: C 67.91, H 4.97, N 2.88.
Phosphanaphthalene2f
Yellow solid, 300 mg, 68 % yield. 31P NMR (121 MHz, CDCl3): δ 13.1 ppm; 1H NMR (300 MHz, CDCl3): δ 2.39 (s, 3H, Me), 3.61 (br s,
3H, OMe), 4.12 (s, 3H, OMe), 6.85 (td, J = 1.8, 8.1 Hz, 1H), 7.17 (dd, J = 8.1, 12.6 Hz, 1H), 7.44-7.57 (m, 6H), 7.63-7.75 (m, 5H); 13
NMR (75 MHz, CDCl3): δ 21.72 (s, CH3), 45.57 (d, JCP = 114.0 Hz, P=C), 50.42 (s, CH3, OMe), 57.81 (s, CH3, OMe), 105.46 (d, JCP
C
=
92.3 Hz, C), 116.14 (d, JCP = 7.5 Hz, C), 121.40 (d, JCP = 8.3 Hz, CH), 124.53 (d, JCP = 12.8 Hz, CH), 127.58 (d, JCP = 95.3 Hz, 2C), 128.59
(d, JCP = 12.8 Hz, 4CH), 131.89 (d, JCP = 3.8 Hz, 2CH), 132.68 (d, JCP = 9.0 Hz, CH), 133.14 (d, JCP = 10.5 Hz, 4CH), 136.32 (d, JCP = 6.8
Hz, C), 142.98 (d, JCP = 2.3 Hz, C), 145.80 (d, JCP = 21.8 Hz, C), 159.25 (s, C), 166.13 (b, CO2). HRMS calcd for C26H23NO4P [M+H]+:
444.1359; found : 444.1353.
Phosphanaphthalene2g
Red solid, 150 mg,33% yield). 31P NMR (121 MHz, CDCl3): δ 13.6 ppm; 1H NMR (300 MHz, CDCl3): δ 3.55 (br s, 3H, OMe), 4.13 (s,
3H, OMe), 7.33-7.36 (m, 1H), 7.48-7.63 (m, 7H), 7.89-7.96 (m, 4H), 8.07-8.11 (m, 1H); 13C NMR (75 MHz, CDCl3): δ 48.86 (d, JCP
121.5 Hz, P=C), 50.61 (br s, CH3, OMe), 58.00 (s, CH3, OMe), 107.21 (d, JCP = 87.8 Hz, C), 115.32 (d, JCP = 6.0 Hz, C), 115.57 (d, JCP
=
=
5.3 Hz, C), 117.51 (d, JCP = 6.0 Hz, C), 126.14 (d, JCP = 93.0 Hz, 2C), 126.22 (d, JCP = 6.8 Hz, CH), 128.75 (d, JCP = 13.5 Hz, 4CH), 130.75
(d, JCP = 8.3 Hz, CH), 131.50 (d, JCP = 1.5 Hz, CH), 132.57 (d, JCP = 3.0 Hz, 2CH), 133.64 (d, JCP = 11.3 Hz, 4CH), 137.44 (d, JCP = 4.5 Hz,
C), 147.21 (d, JCP = 21.8 Hz, C), 159.28 (s, C), 165.32 (b, CO2). HRMS calcd for C26H20N2O4P [M+H]+: 455.1155; found : 455.1155
Phosphanaphthalene2h
Yellow solid, 184 mg, 41 % yield. 31P NMR (121 MHz, CDCl3): δ 13.6 ppm; 1H NMR (300 MHz, CDCl3): δ 3.60 (br s, 3H, OMe), 4.11
(s, 3H, OMe), 6.90-6.98 (m, 1H), 7.18-7.27 (m, 1H), 7.48-7.85 (m, 11H)；13C NMR (75 MHz, CDCl3): δ 44.67 (d, JCP = 120.8 Hz, P=C),
50.51 (s, CH3, OMe), 57.84 (s, CH3, OMe), 109.39 (d, JCP = 88.5 Hz, C), 115.82 (s, C), 118.02 (dd, J = 9.8, 23.5 Hz, CH), 120.52 (dd, J
= 2.3, 22.5 Hz, CH), 123.56 (dd, J = 7.5, 9.8 Hz, CH), 126.83 (d, JCP = 94.5 Hz, 2C), 128.78 (d, JCP = 13.5 Hz, 4CH), 132.21 (d, JCP = 3.0
Hz, 2CH), 133.07 (d, JCP = 11.3 Hz, 4CH), 144.94 (d, JCP = 21.8 Hz, C), 158.60 (dd, J = 16.5, 243.8 Hz, C), 159.29 (s, C), 165.85 (b,
CO2). One carbon is missing. HRMS: m/z calcd for C25H20FNO4P [M+H]+: 448.1114; found : 448.1113.
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10.1002/ejic.201700011
European Journal of Inorganic Chemistry
Phosphanaphthalene2i
Yellow solid, 225 mg, 49 % yield. 31P NMR (121 MHz, CDCl3): δ 13.4 ppm; 1H NMR (300 MHz, CDCl3): δ 3.60 (br s, 3H, OMe), 4.11
(s, 3H, OMe), 6.94 (dt, J = 2.1, 8.4 Hz, 1H), 7.14-7.21 (m, 1H), 7.46-7.58 (m, 6H), 7.66-7.80 (m, 5H); 13C NMR (75 MHz, CDCl3): δ
46.09 (d, JCP = 120.0 Hz, P=C), 50.58 (s, CH3, OMe), 57.95 (s, CH3, OMe), 106.15 (d, JCP = 91.5 Hz, C), 115.53 (d, JCP = 5.3 Hz, C),
120.77 (d, JCP = 9.0 Hz, CH), 123.06 (d, JCP = 12.8 Hz, CH), 127.05 (d, JCP = 93.8 Hz, 2C), 128.77 (d, JCP = 12.8 Hz, 4CH), 138.20 (d, JCP
= 3.0 Hz, 2CH), 133.07 (d, JCP = 10.5 Hz, 4CH), 134.08 (d, JCP = 9.0 Hz, CH), 137.54 (d, JCP = 6.8 Hz, C), 139.12 (d, JCP = 3.0 Hz, C),
146.88 (d, JCP = 23.3 Hz, C), 159.31 (s, C), 165.72 (b, CO2). HRMS calcd for C25H20ClNO4P [M+H]+: 464.0813; found : 464.0806.
Thienophosphinine2j
Yellow solid, 96 mg, 22 % yield. 31P NMR (121 MHz, CDCl3): δ 10.3 ppm; 1H NMR (300 MHz, CDCl3): δ 3.64 (br s, 3H, OMe), 4.12 (s,
3H, OMe), 7.44-7.55 (m, 7H), 7.67-7.74 (m, 5H); 13C NMR (75 MHz, CDCl3): δ 46.20 (d, JCP = 125.3 Hz, P=C), 50.65 (s, CH3, OMe),
57.87 (s, CH3, OMe), 99.40 (d, JCP = 102.0 Hz, C), 115.32 (d, JCP = 3.8 Hz, C), 122.93 (d, JCP = 10.5 Hz, CH), 127.23 (d, JCP = 96.0 Hz,
2C), 128.38 (d, JCP = 13.5 Hz, 4CH), 131.87 (d, JCP = 3.0 Hz, 2CH), 132.84 (d, JCP = 11.3 Hz, 4CH), 135.24 (d, JCP = 6.8 Hz, CH), 144.65
(d, JCP = 6.8 Hz, C), 146.71 (d, JCP = 24.0 Hz, C), 159.00 (s, C), 166.49 (b, CO2). HRMS calcd for C23H19NO4PS [M+H]+: 436.0767; found
: 436.0769.
Phosphaquinoline2k
Yellow solid, 95 mg, 7 % yield. 31P NMR (121 MHz, CDCl3): δ 24.9 ppm; 1H NMR (300 MHz, CDCl3): δ 1.13-1.42 (m, 9H), 1.65-1.77
(m, 9H), 2.04 (m, 2H), 2.97 (d, JHP = 11.4 Hz, 2H), 3.76 (s, 3H, OMe), 4.06 (s, 3H, OMe), 7.25-7.29 (m, 1H), 7.82-7.86 (m, 1H), 8.30
(d, J= 3.9 Hz, 1H); 13C NMR (75 MHz, CDCl3): δ 25.82 (d, JCP = 0.8 Hz, 2CH2), 26.64 (s, 2CH2), 26.67 (d, JCP = 22.5 Hz, 2CH2), 26.69 (s,
2CH2), 27.34 (d, JCP = 2.3 Hz, 2CH2), 35.25 (d, JCP = 51.0 Hz, 2CH), 43.08 (d, JCP = 104.3 Hz, P=C), 50.48 (s, CH3, OMe), 57.68 (s, CH3,
OMe), 112.78 (s, C), 125.54 (d, JCP = 2.3 Hz, CH), 126.95 (d, JCP = 6.0 Hz, CH), 133.01 (d, JCP = 105.0 Hz, C), 135.68 (d, JCP = 13.5 Hz,
C), 144.19 (d, JCP = 17.3 Hz, CH), 147.75 (d, JCP = 18.8 Hz, C), 159.03 (s, C), 166.89 (s, CO2). HRMS calcd for C24H32N2O4P [M+H]+:
443.2094; found : 443.1833. Anal. Calcd for C24H31N2O4P: C 65.14, H 7.06, N 6.33; found: C 64.76, H 7.21, N 6.52.
Phosphanaphthalene2l
Yellow solid, 435 mg, 32 % yield. 31P NMR (121 MHz, CDCl3): δ 35.0 ppm; 1H NMR (300 MHz, CDCl3): δ 1.02 (t, J = 7.2 Hz, 6H, 2CH3),
3.00-3.17 (m, 4H, 2CH2), 3.65 (s, 3H, OMe), 4.12 (s, 3H, OMe), 7.03-7.09 (m, 1H), 7.44-7.50 (m, 4H), 7.53-7.59 (m, 1H), 7.75-7.84
(m, 3H); 13C NMR (75 MHz, CDCl3): δ13.30 (d, JCP = 4.5 Hz, 2CH3), 39.99 (d, JCP = 3.8 Hz, 2CH2), 50.31 (s, CH3, OMe), 52.69 (d, JCP
=
123.8 Hz, P=C), 57.76 (s, CH3, OMe), 111.47 (d, JCP = 105.8 Hz, C), 116.16 (d, JCP = 6.8 Hz, C), 121.39 (d, JCP = 9.0 Hz, CH), 122.52 (d,
JCP = 12.0 Hz, CH), 127.62 (d, JCP = 124.5 Hz, C), 128.54 (d, JCP = 13.5 Hz, 2CH), 131.20 (d, JCP = 6.8 Hz, CH), 131.67 (d, JCP = 4.5 Hz,
CH), 131.68 (s, CH), 132.93 (d, JCP = 10.5 Hz, 2CH), 135.74 (d, JCP = 7.5 Hz, C), 146.11 (d, JCP = 24.0 Hz, C), 159.31 (s, C), 166.36 (d,
JCP = 6.8 Hz, CO2). HRMS calcd for C23H26N2O4P [M+H]+: 425.1625; found : 425.1621.
Phosphinine2m
1
Yellow solid, 860 mg, 31 % yield. 31P NMR (121 MHz, CDCl3): δ 14.8 ppm; H NMR (300 MHz, CDCl3): δ 1.67-1.74 (m, CH2, 4H),
1.94-1.96 (m, CH2, 2H), 2.77-2.79 (m, CH2, 2H), 3.55 (s, 3H, OMe), 4.04 (s, 3H, OMe), 7.45-7.54 (m, 6H), 7.64-7.72 (m, 4H); 13C
NMR (75 MHz, CDCl3): δ 21.73 (s, CH2), 22.83 (d, JCP = 9.0 Hz, CH2), 24.72 (d, JCP = 9.0 Hz, CH2), 27.06 (d, JCP = 10.5 Hz, CH2), 49.21
(d, JCP = 115.5 Hz, P=C), 50.36 (s, CH3, OMe), 57.70 (s, CH3, OMe), 91.89 (d, JCP = 86.3 Hz, C), 117.60 (d, JCP = 11.3 Hz, C), 125.62 (d,
JCP = 92.3 Hz, 2C), 128.29 (d, JCP = 12.8 Hz, 4CH), 131.29 (d, JCP = 3.0 Hz, 2CH), 133.07 (d, JCP = 10.5 Hz, 4CH), 145.77 (d, JCP = 4.5 Hz,
C), 147.19 (d, JCP = 23.3 Hz, C), 158.18 (s, C), 165.97 (b, CO2). HRMS calcd for C25H25NO4P [M+H]+: 434.1516; found : 434.1478.
Anal. Calcd for C25H24NO4P: C 69.28, H 5.58, N 3.23; found: C 68.93, H 5.64, N 2.96.
Phosphanaphthalene2n
Yellow solid, 131 mg, 33 % yield). 31P NMR (121 MHz, CDCl3): δ 9.5 ppm; 1H NMR (300 MHz, CDCl3): δ 2.48 (s, 3H, Me), 2.55 (s, 3H,
Me), 7.04 (t, J= 7.2 Hz, 1H), 7.26-7.32 (m, 1H), 7.44-7.52 (m, 7H), 7.72-7.79 (m, 4H), 7.93(dd, J= 4.2, 7.8 Hz, 1H); 13C NMR (75 MHz,
CDCl3): δ 14.11 (s, CH3), 28.35 (d, JCP = 9.0 Hz, OMe), 64.32 (d, JCP = 110.3 Hz, P=C), 110.37 (d, JCP = 84.8 Hz, C), 118.22 (d, JCP = 5.3
Hz, C), 121.67 (d, JCP = 8.3 Hz, CH), 123.73 (d, JCP = 12.8 Hz, CH), 126.56 (d, JCP = 95.3 Hz, 2C), 128.57 (d, JCP = 13.5 Hz, 4CH), 131.77
(d, JCP = 3.0 Hz, 2CH), 132.27 (d, JCP = 1.5 Hz, CH), 133.12 (d, JCP = 11.3 Hz, 4CH), 133.20 (d, JCP = 8.3 Hz, CH), 136.46 (d, JCP = 6.0 Hz,
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10.1002/ejic.201700011
European Journal of Inorganic Chemistry
C), 148.96 (d, JCP = 25.5 Hz, C), 155.87 (s, C), 188.56 (s, CO). HRMS calcd for C25H21NO2P [M+H]+: 398.1304; found : 398.1304. Anal.
Calcd for C25H20NO2P: C 75.56, H 5.07, N 3.52; found: C 75.92, H 5.12, N 3.39.
Tervalentphosphanaphthalene6 and its cycloadduct7
The compound 2d (500 mg, 1.28 mmol) was heated at 260 oC in anhydrous toluene for 2h. After the disappearance of 2d
(monitored by 31P NMR), 2,3-dimethyl-1,3-butadiene (260 l, 2.2 mmol) was added and the mixture was stirred for another 1 h
o
at room temperature . Then S8 was added, the reaction mixture was stirred for another 2 h at 60 C. After evaporation of the
solvent, the crude mixture was chromatographed on silica gel with petroleum ether/ethyl acetate (4:1) as eluent to give 7 (Yellow
solid, 120 mg, 24 % yield). 31P NMR (121 MHz, CDCl3): δ 34.6 ppm; 1H NMR (300 MHz, CDCl3): δ 1.64 (s, CH3), 1.77 (s, CH3), 2.54
(t, J= 16.5 Hz, 1H), 2.90-3.05 (m, 2H), 3.28-3.37 (m, 1H), 3.56(s, 3H), 3.62(s, 3H), 7.47-7.51 (m, 1H), 7.58-7.60 (m, 2H), 8.16-8.23
(m, 1H); 13C NMR (75 MHz, CDCl3): δ 20.47 (d, JCP = 1.5 Hz, Me), 21.19 (d, JCP = 11.3 Hz, Me), 31.27 (d, JCP = 3.8 Hz, CH2), 31.86 (s,
Me), 39.2 (d, JCP = 53.3 Hz, CH2), 47.2 (d, JCP = 44.3 Hz, C), 53.43 (s, OMe), 120.68 (d, JCP = 6.8 Hz, C), 121.90 (d, JCP = 7.5 Hz, CH),
124.00 (d, JCP = 9.8 Hz, C), 125.93 (d, JCP = 10.5 Hz, C), 126.70 (d, JCP = 75.8 Hz, C), 126.97 (d, JCP = 3.8 Hz, C), 128.81 (d, JCP = 13.5
Hz, CH), 132.59 (d, JCP = 3.0 Hz, CH), 133.34 (s, C), 133.90 (d, JCP = 10.5 Hz, CH), 155.12 (s, C),166.86 (d, JCP = 5.3 Hz, C). HRMS calcd
for C19H21NO4PS [M+H]+: 390.0923; found : 390.0932. Anal. Calcd for C25H20NO4P: C 69.93, H 4.69, N 3.26; found: C 69.779, H
4.625, N 3.149. Anal. Calcd for C19H20NO4PS: C 58.60, H 5.18, N 3.60; found: C 58.46, H 5.31, N 3.39.
Supplementary information available:
X-ray data for 2a: CCDC no 1450169, 2c: CCDC no 1471158 and 7: CCDC no 1511014.
UV-vis absorption and fluorescence spectra of 2a-2e and NMR spectra of all compounds.
Acknowledgements
This work was supported by the National Natural Science Foundation (21672193,21272218), Specialized Research
Fund for the Doctoral Program of Higher Education (20134101110004) and Zhengzhou University of China.
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