Copper-Catalyzed Oxidative Alkylation (Methylation) of Phosphonamides and Phosphinamides Using Dicumyl Peroxide

Article abstract of DOI:10.1021/acs.joc.7b01527

An effective and practical CuI-catalyzed methodology toward N-alkyl or N-methyl phosphonamides and phosphinamides was herein demonstrated. The transformation took place readily under the oxidative conditions, and plenty of N-alkylated (methylated) amides

Full text of DOI:10.1021/acs.joc.7b01527

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Article
Copper-catalyzed Oxidative Alkylation (Methylation) of
Phosphonamides and Phosphinamides by Using Dicumyl Perxide
Jing Xiao, Qiong Su, Wanrong Dong, Zhihong Peng, Yingjun Zhang, and Delie An
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.7b01527 • Publication Date (Web): 23 Aug 2017
Downloaded from http://pubs.acs.org on August 23, 2017
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Copper-catalyzed Oxidative Alkylation (Methylation) of
Phosphonamides and Phosphinamides by Using
Dicumyl Perxide
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Jing Xiao,a Qiong Su,a Wanrong Dong,*,a Zhihong Peng,*,a Yingjun Zhangb and Delie An*,a
a State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical
Engineering, Hunan University, Changsha 410082, P. R. China;
b State Key Laboratory of Anti-Infective Drug Development (NO. 2015DQ780357), Sunshine Lake
Pharma Co.,Ltd, Dongguan 523871, P. R. China.
e-mails: wanrongdong@hnu.edu.cn; pzh7251@hnu.edu.cn; deliean@hnu.edu.cn.
RECEIVED DATE (to be automatically inserted after your manuscript is accepted if required
according to the journal that you are submitting your paper to)
ABSTRACT
An effective and practical CuI-catalyzed methodology towards N-alkyl or N-methyl phosphonamides
and phosphinamides was herein demonstrated. The transformation took place readily under the
oxidative conditions, and plenty of N-alkylated (methylated) amides (30 examples) were successfully
furnished in high efficiency (up to 92% yields). Dicumyl peroxide was considered to act either as the
oxidant for the alkylation reaction, or methyl donator for the methylation protocol.
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INTRODUCTION
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Phosphonamides and phosphinamides, which represents typical amino-fused organophosphorus
compounds,1 have gained increasing interests due to not only the unique structures, but also the
distinguished properties in pharmaceutical applications and material science.2 As well, the chiral P-
centered modules have been successfully designed for enantioselective sysnthesis.3 Apart from this, they
have been considered as pivotal intermediates for formations of heterocycles such as benzazaphosphole-
1-oxides and phosphaisoquinolin-1-oxides4 which were biologically active molecules. Thus,
considerable attention has been paid for the derivations of the versatile compounds. And, rapid growth
has been gained on the motifs ever since the first example of direct arylation of phosphinamides by aryl
iodides with assistance of Cu(I)-catalysis.5 Howbeit, methodologies for alkylation (methylation) by
using inactive alkanes, have never been reported due to the instabilities of the P-N bonds.6 Therefore, it
is still highly required for alkylation (methylation) of phosphonamides and phosphinamide because of
the magic methyl effect7 and subsequent medicinal explorations. Typically, reactions between
phosphoryl chlorides and alkyl amines were invovled for the synthesis of N-alkyl products, releasing
halo wastes.8 Beware of that, protocols employing peroxides, which could act as multiple roles as either
the oxidant9 for the coupling of nucleophiles, or methyl donators,10-12 which have been well-established
for the formations of C-C,10 C-O11 and C-N12 bonds. Herein we also wished to disclose an effective and
practical method towards N-alkyl (methyl) phosphonamides or phosphinamides in a Cu-catalysis. The
novel method featured for (1) effective flexible mono alkylation/methylation in a step/atomic-economic
fasion in the presence of DCP (dicumyl peroxide) and (2) P-N bonds' maintainabilities under the
oxidative conditions.
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RESULTS AND DISCUSSION
Firstly, diphenyl phosphinamide (1a) and cyclohexane (2a) were chosen as the model substrates for the
optimization of the conditions as summarized in Table 1. To our delight, 1,10-phenanthroline-liganded
CuI made the coupling reaction take place in the presence of DTBP (di-tert butyl peroxide), and the
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desired N-alkylated phosphinamide 3aa was successfully isolated in 74% yield (entry 1). However,
other oxidants, such as TBHP (tert-butyl hydroperoxide, 70% in water, entry 2), K2S2O8 (entry 3),
Ag2CO3 (entry 4) and DDQ (2,3-dicyano-5,6-dichlorobenzoquinone for entry 5) failed to make the
alkylation reaction occur except DCP (dicumyl peroxide for entry 6), which enabled the occurance of
the reaction in high efficiency, up to 90% yield after isolation. Screening on the ligands proved that
1,10-phenanthroline was crucial to the useful transformation because only trace product was observed in
the presence of TMEDA (tetramethyl ethylenediamine for entry 7) and DMEDA (dimethyl
ethanediamine for entry 8) or even no reaction was detected in the absence of any ligands (entry 9).
Other copper or copprus catalysts, for example, CuBr, CuCl2 and Cu(OAc)2 offered inferior
performance to CuI did, for 3aa was isolated in yields ranging from 58% to 78% (entries 10 – 12).
Ferric-catalysts, exemplfied by FeCl3 and other organo-catalyts such as TBAI (tetra-tert-butyl
ammonium iodide) and elemental iodine were found totally useless to the transformation (entries 13 to
15).
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Table 1. Conditions Optimizationa
Entry
1
Cat.
CuI
Ligand
Phenb
Phenb
Phenb
Phenb
Phenb
Phenb
TMEDA
DMEDA
--
[O]
DTBP
TBHP
K2S2O8
Ag2CO3
DDQ
DCP
DCP
Yieldc
74%
n.d.d
n.d.
2
CuI
3
CuI
4
CuI
n.d.
5
CuI
n.d.
6
CuI
90%
trace
trace
n.d.
7
CuI
8
CuI
DCP
9
CuI
DCP
10
11
12
13
CuBr
CuCl2
Cu(OAc)2
FeCl3
Phenb
Phenb
Phenb
Phenb
DCP
78%
72%
58%
n.d.
DCP
DCP
DCP
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TBAI
I2
--
--
DCP
DCP
n.d.
n.d.
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a1a (0.2 mmol), 2a (2.0 mL, ca. 20 mmol), Cat. (10 mol%), Ligand (10 mol%), 4 Å MS (powdered, 200 wt%),
[O] (2.0 equiv.) at 140 oC in sealed tube for 12 h. bstands for 1,10-phenanthroline. bIsolated yields.dstands for not
detected.
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With the optimized reaction conditions successfully established, substrate scope and limitations of
phosphonamides and phosphinamides were evaluated as summarized in Table 2. It was found that P-
alkoxyl phosphonamides were compatible in the CuI-mediated system. For example, P-methoxy-, P-
ethoxy-, P-isopropoxy- and P-n-butoxy-P-phenyl phosphonamides (1b – 1e) coupled freely with 2a,
furnishing the desired N-cyclohexyl phosphonamides 3ba – 3ea in yields ranging from 78% to 82%
(entries 1 – 4). In the similar pattern, P-methoxyethoxy-P-phenyl phosphonamide 1f and P-
chloropropoxy-P-phosphonamide 1g reacted with 2a under oxidative conditions, providing the
corresponding N-alkylated phosphonamides 3fa and 3ga in 76% and 88% yields, respectively (entries 5
and 6). Subsequently, the tolerance of (un)substituted benzyloxy groups were also checked in the
protocol. Luckily, P-benzyloxy- (entry 7), P-(3-fluorobenzyloxy)- (entry 8), P-(4-chlorobenzyloxy)-
(entry 9) amd P-(2-bromobenzyloxy)- (entry 10) P-phenyl phosphonamides 1h – 1k underwent the
alkylation reaction smoothly under the Cu(I)-catalysis, giving the N-cyclohexylated products 3ha – 3ka
in yields from 75% to 90%. Also, P,P-di-(p-tolyl) phosphinamide (1l) and P,P-di-(2-thiophenyl)
phosphinamide (1m) coupled with 2a readily, offering the desired N-alkyl phosphinamides 3la and 3ma
in 85% and 78% yields, respectively (entries 11 and 12). Moreover, the activities of N-monosubstituted
phosphinamides were also examined in the system. And N-methyl-P,P-diphenyl phosphinamide (1n)
furnished the desired N-dialkyl phosphinamide 3na in 48% yield, while N,P,P-triphenyl phosphinamide
(1o) offered the corresponding N-cyclohexyl product 3oa in 79% yield (entries 13 and 14).
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Table 2. Scope of Phosphonamides and Phosphinamidesa
O
O
R'
R'
CuI/Phen
H
Ar
P N
+
P N
Ar
4 Å MS, DCP
H
R
R
140 oC, 12 h
1b - 1o
2a
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Entry
Ar
C6H5
R
R'
H
Yieldb
85%
80%
78%
82%
76%
88%
81%
76%
90%
75%
85%
78%
48%
79%
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2
CH3O
3ba
3ca
3da
3ea
3fa
3ga
3ha
3ia
C6H5
C2H5O
H
3
C6H5
iPrO
H
4
C6H5
C4H9O
H
5
C6H5
CH3O(CH2)2O
Cl(CH2)3O
C6H5CH2O
3-FC6H4CH2O
4-ClC6H4CH2O
2-BrC6H4CH2O
4-CH3C6H4
2-Thiophenyl
Ph
H
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C6H5
H
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C6H5
H
8
C6H5
H
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C6H5
H
3ja
3ka
3la
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C6H5
H
4-CH3C6H4
2-Thiophenyl
Ph
H
H
3ma
3na
3oa
CH3
C6H5
Ph
Ph
a1a (0.5 mmol), 2a (5.0 mL, ca. 50 mmol), CuI (10 mol%), Phen (10 mol%), 4 Å MS (powdered, 200 wt%), DCP (2.0
equiv.) at 140 oC in sealed tube for 12 h. bIsolated yields.
The activities of various alkanes for the coupling reaction were also tested in the copper-catalysis as
shown in Scheme 1. Except cyclohaxane, cyclopentane (2b), cycloheptane (2c) and cyclooctane (2d)
coupled with P,P-diphenyl phosphinamide (1a) freely, and different N-cycloalkyl-P,P-diphenyl
phosphinamides 3ab – 3ad in 65% - 86% yields. Chained hexane (2e) underwent the alkylation reaction
with P,P-diphenyl phosphinamide (1a), offering N-2-hexyl phosphinamide (3ae) and N-3-hexyl
phosphinamide (3ae') in a combined 75% yield with a 1:1 ratio (by 1H-NMR calculation).
Scheme 1. Scope of alkanesa
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a1a (0.5 mmol), 2a (5.0 mL, ca. 50 mmol), CuI (10 mol%), Phen (10 mol%), 4 Å MS (powdered, 200 wt%), DCP (2.0
equiv.) at 140 oC in sealed tube for 12 h. bIsolated yields.
Inspired by the good results of the intermolecular alkylation reactions, intramolecular alkylation was
designed on the substrates of P-cyclohexyloxy-P-phenyl phosphonamides (1p) and P-
cyclohexylmethoxy-P-phenyl phosphonamides (1q) for the construction of five or six-membered O-P-
N-backboned heterocyclic compounds (Scheme 2).
Scheme 2. Unexpected Methylation Reactions
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However, beyond our expectations, intramolecular coupling failed to happen under the oxidative
1
2
conditions, even in the presence of other organic oxidants, such as AIBN (azobisisobutyronitrile), BPO
(Dibenzoyl peroxide), DTBP or DDQ. Instead, N-methylated phosphonamides 4p and 4q were obtained
successfully in 80% and 76% yields after separation, in which the oxidant DCP was considered to act as
the methyl provider in the reaction.12
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Under the modified conditions, the scope of the substrates was evaluated as shown in Table 3.
Phosphinamide 1a was readily methylated and corresponding product 4a was isolated in 88% yield
(entry 1). Chained alkoxy decorated phosphonamides, for instance, methoxy (entry 2), ethoxy (entry 3),
isopropoxy (entry 4), n-butoxy (entry 5), methoxyethoxy (entry 6) and chloropropoxy (entry 7) were
well-compatible in the system and the desired products 4b – 4g were separated in yields from 80% to
90%. Similarly, (un)substituted benzyl fused phosphonamides also were coupled with DCP and N-
methylated molecules 4h – 4k were furnished in 67% - 82% yields (entries 8 – 11). Other
phosphinamides, such as P,P-di-(p-tolyl) (entry 12) and P,P-di-(2-thiophenyl) (entry 13)
phosphinamides 1l and 1m were successfully methylated under the oxidative conditions, providing the
corresponding products 4l and 4m in 82% and 76% yields, respectively.
Table 3. Scope of Phosphonamides and Phosphinamidesa
Entry
Ar
R
C6H5
Yieldb
88%
90%
85%
86%
92%
82%
80%
82%
68%
1/4
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2
3
4
5
6
7
8
9
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
1a/4a
1b/4b
1c/4c
1d/4d
1e/4e
1f/4f
CH3O
C2H5O
iPrO
C4H9O
CH3O(CH2)2O
Cl(CH2)3O
C6H5CH2O
3-FC6H4CH2O
1g/4g
1h/4h
1i/4i
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C6H5
C6H5
4-ClC6H4CH2O
2-BrC6H4CH2O
4-CH3C6H4
72%
67%
88%
78%
1j/4j
1k/4k
1l/4l
1
2
3
4
5
6
7
4-CH3C6H4
2-Thiophenyl
2-Thiophenyl
1m/4m
a1 (0.5 mmol), CuI (10 mol%), Phen (10 mol%), 4 Å MS (powdered, 200 wt%), DCP (2.0 equiv.) in benzene (3.5
mL) at 140 oC in sealed tube for 12 h. bIsolated yields.
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9
Subsequently, competitive reactions were carried out as shown in Scheme 3. P,P-diphenyl
phosphinamide (1a) and P-phenyl-P-methoxy phosphonamide (1b) were mixed in an equal equivalent
(0.25 mmol) to react with 2a (3.5 mL) to check the difference in the potencies of the amino groups.
After 5 hours, the N-cyclohexy products 3aa and 3ba were isolated in 42% and 39% yields, respectively,
indicating that the two amino groups exhibited almost the same activities in the protocol (Eq. 1)).
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Scheme 3. Competitive reactions
It was noteworthy that reaction between 1a and a mixture of 2a (2.0 mL) and 2d (2.0 mL) providing
trace 3aa while 3ad was isolated in 35% and 60% yields for 5 and 12 hours, respectively (Eq. 2)).
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Involvement of 2a under the standard conditions of methylation reaction (Eq. 3)), formation of 4a was
depressed significantly while N-cyclohexyl product 3aa was isolated smoothly in 70% yield. The results
of Eq. B and Eq. C might be relative to the difference in the stabilities of the radical particles which
were generated in the system.11a
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To take a deeper insight into the CuI-mediated alkylation (methylation) reactions, control reactions
between 1a and 2a were conducted for better understandings (Scheme 4). Additions of either TEMPO
(2,2,6,6-tetramethylpiperidine 1-oxyl) or BHT (butylated hydroxytoluene) as the radical particle
scavangers to the reactions depressed the formation of 3aa or 4a significantly, for only trace of the
desired products were observed after 12 h. However, attempts for the isolation of the TEMPO-adducts
failed probably due to the instabilities of the intermediates in the system.
Scheme 4. Control reactions
2a
O
O
CuI/Phen
P NH2
O
P NH
O
4 Å MS, DCP
H3C
H3C
140 oC, 12 h
TEMPO or BHT
1a
3aa, trace
O
O
CuI/Phen
P NH2
O
P NH
4 Å MS, DCP
CH3
O
H3C
H3C
140 oC, 12 h, Benezene
TEMPO or BHT
1a
4a, trace
Based on the results of the control reactions and literature explorations,9e,12 plausible radical
mechanism of the coupling protocols, which was exemplified by the reactions of 1a and 2a for the
formations of 3aa and 4a, was proposed as shown in Scheme 5. Firstly, homo-cleavage of DCP took
place easily for the generation of a radical particle I. With the assistance of newly-generated radical
intermediate I, Cu(I) was readily oxidized into a Cu(II) species, leading to another anion particle II.
Meanwhile, rearrangement of the radical particle I allowed the formation of acetophenone and a methyl
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radical particle readily in the system. And cyclohexyl radical particle was facilely generated if the
reaction was conducted in the existence of cyclohexane. Then, the in-situ formed Cu(II) coordinated
with the amide group of the substrate 1a, giving a key intermediate A. Successively, the intermediate A
coupled with the radical particle easily to afford the final N-alkylated product 3aa or 4a, which relied on
the usage of cyclohexane in the system, releasing a Cu(I) for the completion of the catalytic cycle.
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Scheme 5. Plausible mechanism
CONCLUSIONS
In conclusion, we have developed a CuI-catalyzed selective alkylation or methylation of
phosphinamides and phosphonamides in the assistance of dicumyl peroxide, which played multiple
roles as the oxidant or methyl radical source in the transformation. The reaction provided a general
methodology towards kinds of N-alkyl phosphinamides and phosphonamides of great significance in
high yields. And further explorations for the synthetical and clinical applications of the products were
still on-going in our labartory.
EXPERIMENTAL SECTION
General information
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All product mixtures were analyzed by thin layer chromatography glass-backed silica TLC plates with a
fluorescent indicator from Branch of Qingdao Haiyang Chemical CO. LTD. UV-active compounds were
detected with a UV lamp (λ = 254 nm). For flash column chromatography, silica gel (200 - 300 mesh)
was used as stationary phase and a mixture of n-hexane and ethyl acetate was used as eluent. 1H and 13C
NMR spectra were recorded on a Varian INOVA-400 in deuterated chloroform at 25 °C with residue
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solvent peaks as internal standards (δ = 7.26 ppm for H-NMR and δ = 77.16 ppm for 13C-NMR).
Chemical shifts δQare reported in ppm, and spin-spin coupling constants (J) are given in Hz, while
multiplicities are abbreviated by s (singlet), d (doublet), t (triplet), q (quartet) and m (multiplet) and
some C-P couplings were ignored due to complexity. Mass spectra were recorded on a ThermoFinnigan
MAT95XP microspectrometer and High Resolution Mass Spectra (HRMS) were recorded on Agilent
Technologies Accurate Mass Q-TOF 6530 microspectrometer. Melting points were recorded on a
national standard melting point apparatus (Model: Taike XT-4) and were uncorrected.
General procedure for the synthesis of N-alkyl phosphonamides and
phosphinamides 3
A Schlenk tube (35 mL) equipped with a magnetic bar was loaded with the amides 1 (0.25 mmol),
copper iodide (4.8 mg, 0.025 mmol), 1,10-phenanthroline (4.5 mg, 0.025 mmol), dicumyl peroxide (135
mg, 0.5 mmol), and 4 Å molecular sieve (200 wt%) in dry alkane 2 (20 mmol), then the reaction
mixture was allowed to stir at 140 °C for 12 h. After cooling to room temperature, the mixture was
filtered through a short celite pad and washed with dichloromethane (15 mL × 3). The filtrate was
concentrated, and the oily crude product was purified by column chromatography using silica gel (200 –
300 mesh) as stationary phase and a mixture of n-hexane and ethyl acetate (2:1) as eluent to give the N-
alkyl phosphonamides and phosphinamides 3 (Rf = ca.0.3 otherwise noted).
General procedure for the synthesis of N-methyl phosphonamides and
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phosphinamides 4
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A Schlenk tube (35 mL) equipped with a magnetic bar was loaded with the amides 1 (0.25 mmol),
copper iodide (4.8 mg, 0.025 mmol), 1,10-phenanthroline (4.5 mg, 0.025 mmol), dicumyl peroxide (135
mg, 0.5 mmol), and 4 Å molecular sieve (200 wt%) in dry benzene (3.5 mL), then the reaction mixture
was allowed to stir at 140 °C for 12 h. After cooling to room temperature, the mixture was filtered
through a short celite pad and washed with dichloromethane (15 mL × 3). The filtrate was concentrated,
and the oily crude product was purified by column chromatography using silica gel (200 – 300 mesh) as
stationary phase and a mixture of n-hexane and ethyl acetate (1:1) as eluent to give the N-methyl
phosphonamides and phosphinamides 4 (Rf = ca. 0.1 otherwise noted).
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N-Cyclohexyl-P,P-diphenylphosphinic amide (3aa). White solid (54.1 mg, 90%), m.p.: 186 - 189 oC. 1H
NMR (400 MHz, CDCl3) δ = 7.90 (dd, J = 11.7, 7.7 Hz, 4H), 7.52 – 7.39 (m, 6H), 3.08 – 2.92 (m, 1H),
2.83 – 2.70 (m, 1H), 2.12 – 2.01 (m, 2H), 1.73 – 1.60 (m, 2H), 1.53 (d, J = 12.1 Hz, 1H) 1.30 – 1.01 (m,
5H) (ppm). 13C NMR (100 MHz, CDCl3) δ = 133.4 (JC-P = 129.1 Hz), 132.2 (JC-P = 9.4 Hz), 131.8 (JC-P
= 2.8 Hz), 128.6 (JC-P = 12.5 Hz), 50.7 (JC-P = 1.6 Hz), 36.8 (JC-P = 4.9 Hz), 22.5, 25.3 (ppm). 31P NMR
(100 MHz, CDCl3) δ = 22.0 (ppm). IR (in KBr): ν = 3128, 2927, 2856, 1446, 1196, 1097, 993, 916,
692, 573, 515 (cm-1). MS (EI) m/z (%): 77.0 (14), 98.1 (41), 142.0 (13), 201.0 (100), 202.0 (26), 216.0
(32), 256.1 (60), 299.1 (28). HRMS (ESI) (m/z) [M+ H+]: Calcd. for C18H23NOP: 300.1517; Found
300.1512.
N-Cyclohexyl-P-methoxyl-P-phenylphosphonic amide (3ba). White solid (107.3 mg, 85%), m.p.: 85 - 86
1
oC. H NMR (400 MHz, CDCl3) δ = 7.75 (dd, J = 12.7, 7.8 Hz, 2H), 7.48 – 7.33 (m, 3H), 3.65 (d, J =
11.1 Hz, 3H), 2.98 – 2.78 (m, 2H), 1.87 – 1.69 (m, 2H), 1.64 – 1.53 (m, 2H), 1.46 (d, J = 11.6 Hz, 1H),
13
1.23 – 0.99 (m, 5H) (ppm). C NMR (100 MHz, CDCl3) δ = 131.7 (JC-P = 2.7 Hz), 131.4 (JC-P = 9.7
Hz), 131.3 (JC-P = 172.8 Hz), 128.3 (JC-P = 14.2 Hz), 51.0 (JC-P = 5.7 Hz), 49.9, 35.9 (JC-P = 17.8 Hz),
25.3, 25.0 (ppm). 31P NMR (100 MHz, CDCl3) δ = 22.9 (ppm). MS (EI): m/z (%): 98.1 (21), 155.0 (59),
172.1 (14), 210.1 (100), 211.1 (12), 224.1 (7), 253.1 (26), 280.9 (33). IR (in KBr): ν = 3178, 2926,
2851, 1448, 1198, 1082, 972, 918, 692, 568, 525 (cm-1). HRMS (ESI) (m/z) [M + H+]: Calcd. for
C13H21NO2P: 254.1310; Found. 254.1302.
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The Journal of Organic Chemistry
N-Cyclohexyl-P-ethoxyl-P-phenylphosphonic amide (3ca). White solid (106.8 mg, 80%), m.p.: 91 - 92
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oC. H NMR (400 MHz, CDCl3) δ = 7.80 (dd, J = 12.6, 7.5 Hz, 2H), 7.53 – 7.46 (m, 1H), 7.46 – 7.38
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(m, 2H), 4.15 – 4.00 (m, 2H), 3.04 – 2.88 (m, 1H), 2.72 – 2.56 (m, 1H), 1.88 – 1.76 (m, 2H), 1.68 – 1.58
(m, 2H), 1.51 (d, J = 11.9 Hz, 1H), 1.32 (t, J = 7.0 Hz, 3H), 1.28 – 1.01 (m, 5H) (ppm). 13C NMR (100
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MHz, CDCl3) δ = 131.9 (JC-P = 172.3 Hz), 131.7 (JC-P = 2.9 Hz), 131.6 (JC-P = 9.7 Hz), 128.4 (JC-P
=
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14.2 Hz), 60.6 (JC-P = 5.5 Hz), 50.0, 36.1 (JC-P = 13.8 Hz), 25.5, 25.1, 16.5 (JC-P = 6.8 Hz) (ppm). P
NMR (100 MHz, CDCl3) δ = 21.4 (ppm). MS (EI): m/z (%): 77.0 (5), 98.1 (8), 141.0 (17), 186.1 (9),
196.0 (13), 224.1 (100), 225.1 (13), 238.1 (13), 267.1 (33). IR (in KBr): ν = 3190, 2925, 2848, 1453,
1212, 1131, 972, 908, 826, 756, 695, 567, 513 (cm-1). HRMS (ESI) (m/z) [M + H+]: Calcd. for
C14H23NO2P: 268.1466; Found 268.1459.
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N-Cyclohexyl-P-isopropoxyl-P-phenylphosphonic amide (3da). White solid (109.6 mg, 78%), m.p.: 101
- 102 oC. 1H NMR (400 MHz, CDCl3) δ = 7.79 (dd, J = 12.8, 7.5 Hz, 2H), 7.50 – 7.37 (m, 3H), 4.75 –
4.61 (m, 1H), 3.04 – 2.90 (m, 1H), 2.66 – 2.50 (m, 1H), 1.88 – 1.76 (m, 2H), 1.68 – 1.58 (m, 2H), 1.55 –
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1.46 (m, 1H), 1.35 (d, J = 6.1 Hz, 3H), 1.25 (d, J = 6.1 Hz, 3H), 1.23 – 1.03 (m, 5H) (ppm). C NMR
(100 MHz, CDCl3) δ = 132.8 (JC-P = 172.0 Hz), 131.6 (JC-P = 9.7 Hz), 131.6 (JC-P = 3.0 Hz), 128.3 (JC-P
= 14.1 Hz), 69.3 (JC-P = 5.5 Hz), 50.0, 36.1 (JC-P = 6.1 Hz), 25.5, 25.1 (JC-P = 2.2 Hz), 24.4 (JC-P = 4.5
31
Hz), 24.2 (JC-P = 4.1 Hz) (ppm). P NMR (100 MHz, CDCl3) δ = 20.1 (ppm). MS (EI): m/z (%): 56.1
(25), 77.1 (18), 98.1 (47), 141.1 (25), 158.1 (27), 196.1 (100), 238.1 (38), 239.1 (16), 281.1 (18). IR (in
KBr): ν = 3187, 2927, 2840, 1442, 1213, 1108, 1022, 954, 914, 832, 740, 683, 553, 511 (cm-1).
HRMS (ESI) (m/z) [M + H+]: Calcd. for C15H25NO2P: 282.1623; Found 282.1615 .
P-Butoxyl-N-cyclohexyl-P-phenylphosphonic amide (3ea). White solid (120.9 mg, 82%), m.p.: 75 - 77
oC. H NMR (400 MHz, CDCl3) δ = 7.77 (dd, J = 12.6, 7.4 Hz, 2H), 7.49 – 7.43 (m, 1H), 7.43 – 7.35
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(m, 2H), 4.03 – 3.92 (m, 2H), 3.00 – 2.86 (m, 1H), 2.78 – 2.60 (m, 1H), 1.86 – 1.72 (m, 2H), 1.68 – 1.55
(m, 4H), 1.48 (d, J = 11.5 Hz, 1H), 1.43 – 1.32 (m, 2H), 1.26 – 1.00 (m, 5H), 0.89 (t, J = 7.3 Hz, 3H)
13
(ppm). C NMR (100 MHz, CDCl3) δ = 131.9 (JC-P = 172.4 Hz), 131.6 (JC-P = 2.8 Hz), 131.5 (JC-P
=
9.7 Hz), 128.3 (JC-P = 14.1 Hz), 64.2 (JC-P = 5.7 Hz), 50.0, 36.0 (JC-P = 16.8 Hz), 32.6 (JC-P = 6.9 Hz),
25.4, 25.1, 18.9, 13.7 (ppm). 31P NMR (100 MHz, CDCl3) δ = 21.3 (ppm). MS (EI): m/z (%): 56.1 (40),
77.1 (28), 98.1 (86), 141.1 (47), 158.1 (41), 196.1 (89), 252.2 (100), 295.2 (31). IR (in KBr): ν = 3194,
2927, 2850, 1447, 1214, 1125, 1022, 909, 755, 566, 512 (cm-1). HRMS (ESI) (m/z) [M + H+]: Calcd.
For C16H27NO2P: 296.1779; Found 296.1788.
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N-Cyclohexyl-P-(2-methoxyethoxyl)-P-phenylphosphonic amide (3fa): White solid (113.4 mg, 76%),
m.p.: 70 - 71 oC. 1H NMR (400 MHz, CDCl3) δ = 7.80 (dd, J = 12.9, 7.5 Hz, 2H), 7.50 – 7.44 (m, 1H),
7.44 – 7.36 (m, 2H), 4.24 – 4.15 (m, 1H), 4.11 – 4.02 (m, 1H), 3.61 – 3.55 (m, 2H), 3.35 (s, 3H), 3.05 –
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2.84 (m, 2H), 1.87 – 1.76 (m, 2H), 1.66 – 1.56 (m, 2H), 1.49 (d, J = 12.0 Hz, 1H), 1.26 – 1.01 (m, 5H)
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(ppm). C NMR (101 MHz, CDCl3) δ = 131.8 (JC-P = 173.9 Hz), 131.8 (JC-P = 2.9 Hz), 131.6 (JC-P
=
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9.9 Hz), 128.4 (JC-P = 14.3 Hz), 72.0 (JC-P = 6.3 Hz), 63.3 (JC-P = 5.7 Hz), 59.0, 49.9, 36.0 (JC-P = 2.7
Hz), 25.4, 25.0 (ppm). 31P NMR (100 MHz, CDCl3) δ = 22.2 (ppm). MS (EI): m/z (%): 57.1 (22), 59.1
(37), 77.1 (18), 98.1 (64), 140.1 (18), 155.1 (21), 158.1 (23), 196.1 (25), 199.1 (100), 240.1 (19), 254.1
(35), 297.2 (22). IR (in KBr): ν = 3184, 2926, 2848, 1450, 1207, 1126, 1045, 960, 918, 818, 748, 692,
567, 536 (cm-1). HRMS (ESI) (m/z) [M + H+]: Calcd. for C15H25NO3P: 298.1572; Found. 298.1576.
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P-(3-Chloropropoxyl)-N-cyclohexyl-P-phenylphosphonic amide (3ga): White solid (139.1 mg, 88%),
m.p.: 62 - 63 oC. 1H NMR (400 MHz, CDCl3) δ = 7.77 (dd, J = 12.8, 7.3 Hz, 2H), 7.52 – 7.46 (m, 1H),
7.46 – 7.38 (m, 2H), 4.14 (q, J = 6.2 Hz, 2H), 3.65 (t, J = 6.2 Hz, 2H), 3.03 – 2.90 (m, 1H), 2.82 – 2.65
(m, 1H), 2.16 – 2.06 (m, 2H), 1.88 – 1.75 (m, 2H), 1.68 – 1.57 (m, 2H), 1.50 (d, J = 12.1 Hz, 1H), 1.28
– 1.01 (m, 5H) (ppm). 13C NMR (100 MHz, CDCl3) δ = 131.9 (JC-P = 2.9 Hz), 131.5 (JC-P = 172.5 Hz),
131.4 (JC-P = 9.7 Hz), 128.5 (JC-P = 14.2 Hz), 61.0 (JC-P = 5.4 Hz), 50.1, 41.2, 36.0 (JC-P = 16.9 Hz), 33.4
(JC-P = 6.8 Hz), 25.4, 25.1 (ppm). 31P NMR (100 MHz, CDCl3) δ = 21.7 (ppm). MS (EI): m/z (%): 56.1
(9), 77.0 (14), 98.1 (33), 141.0 (35), 196.1 (18), 272.0 (100), 274.0 (33), 315.1 (21), 317.1 (7). IR (in
KBr): ν = 3197, 2924, 2850, 1448, 1213, 1117, 1034, 970, 914, 746, 563 (cm-1). HRMS (ESI) (m/z)[M
+ H+]: Calcd. for C15H24ClNO2P: 316.1233; Found. 316.1226.
P-Benzyloxyl-N-cyclohexyl-P-phenylphosphonic amide (3ha): White solid (133.7 mg, 81%), m.p.: 111 -
o
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112 C. H NMR (400 MHz, CDCl3) δ = 7.82 (dd, J = 12.9, 7.7 Hz, 2H), 7.53 – 7.47 (m, 1H), 7.47 –
7.40 (m, 2H), 7.40 – 7.27 (m, 5H), 5.13 – 4.99 (m, 2H), 3.06 – 2.93 (m, 1H), 2.80 – 2.66 (m, 1H), 1.87 –
1.76 (m, 2H), 1.67 – 1.57 (m, 2H), 1.55 – 1.46 (m, 1H), 1.26 – 1.02 (m, 5H) (ppm). 13C NMR (100 MHz,
CDCl3) δ = 137.0 (JC-P = 7.5 Hz), 131.9 (JC-P = 3.0 Hz), 131.6 (JC-P = 9.8 Hz), 131.6 (JC-P = 172.6 Hz),
128.6, 128.5 (JC-P = 14.3 Hz), 128.2, 127.8, 66.0 (JC-P = 5.2 Hz), 50.1, 36.0 (JC-P = 14.8 Hz), 25.4, 25.1
31
(ppm). P NMR (100 MHz, CDCl3) δ = 22.1 (ppm). MS (EI): m/z (%): 65.1 (6), 91.1 (68), 98.1 (10),
141.0 (8), 158.1 (5), 238.1 (100), 239.1 (14), 286.1 (46), 287.1 (8), 329.2 (21). IR (in KBr): ν = 3160,
2928, 2851, 1452, 1213, 1122, 1038, 924, 852, 788, 748, 689, 553, 512 (cm-1). HRMS (ESI) (m/z) [M +
H+]: Calcd. for C19H24NO2P: 330.1623; Found. 330.1629.
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N-Cyclohexyl-P-(3-fluorobenzyloxyl)-P-phenylphosphonic amide (3ia): White solid (131.4 mg, 76%),
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m.p.: 101 - 102 C. H NMR (400 MHz, CDCl3) δ = 7.83 (dd, J = 13.0, 7.3 Hz, 2H), 7.55 – 7.48 (m,
1H), 7.48 – 7.41 (m, 2H), 7.34 – 7.27 (m, 1H), 7.17 – 7.06 (m, 2H), 7.04 – 6.95 (m, 1H), 5.12 – 4.98 (m,
2H), 3.08 – 2.94 (m, 1H), 2.87 – 2.70 (m, 1H), 1.88 – 1.77 (m, 2H), 1.68 – 1.59 (m, 2H), 1.56 – 1.48 (m,
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1H), 1.27 – 1.04 (m, 5H) (ppm). 13C NMR (100 MHz, CDCl3) δ = 163.0 (JC-F = 246.3 Hz), 139.6 (JC-P
7.5 Hz), 132.0 (JC-P = 3.0 Hz), 131.6 (JC-P = 9.8 Hz), 131.3 (JC-P = 172.6 Hz), 130.2 (JC-P = 8.2 Hz),
=
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128.5 (JC-P = 14.3 Hz), 123.0 (JC-P = 3.0 Hz), 115.0 (JC-P = 21.1 Hz), 114.4 (JC-P = 22.1 Hz), 65.1 (JC-P
=
19
5.0 Hz), 50.1, 36.0 (JC-P = 15.8 Hz), 25.4, 25.1 (ppm). F NMR (376 MHz, CDCl3) δ = -112.8 (ppm).
31P NMR (100 MHz, CDCl3) δ = 22.3 (ppm). MS (EI): m/z (%): 56.1 (11), 77.1 (11), 98.1 (22), 109.1
(83), 141.1 (13), 158.1 (13), 196.1 (20), 238.1 (100), 239.1 (17), 304.1 (60), 347.2 (19). IR (in KBr): ν =
3167, 2927, 2852, 1591, 1454, 1211, 1132, 1034, 922, 854, 787, 744, 688, 548, 511 (cm-1).
HRMS (ESI) (m/z) [M + H+]: Calcd. for C19H23FNO2P: 348.1529; Found. 348.1535.
P-(4-Chlorobenzyloxyl)-N-cyclohexyl-P-phenylphosphonic amide (3ja): White solid (163.3 mg, 90%),
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m.p.: 114 - 115 C. H NMR (400 MHz, CDCl3) δ = 7.80 (dd, J = 12.9, 7.7 Hz, 2H), 7.55 – 7.48 (m,
1H), 7.47 – 7.40 (m, 2H), 7.31 (bs, 4H), 5.08 – 4.96 (m, 2H), 3.05 – 2.92 (m, 1H), 2.76 – 2.63 (m, 1H),
13
1.87 – 1.76 (m, 2H), 1.68 – 1.58 (m, 2H), 1.55 – 1.47 (m, 1H), 1.28 – 1.03 (m, 5H) (ppm). C NMR
(100 MHz, CDCl3) δ = 135.5 (JC-P = 7.2 Hz), 134.1, 132.0 (JC-P = 3.0 Hz), 131.6 (JC-P = 9.8 Hz), 131.3
(JC-P = 172.5 Hz), 129.2, 128.8, 128.6 (JC-P = 14.3 Hz), 65.2 (JC-P = 5.1 Hz), 50.1, 36.0 (JC-P = 15.3 Hz),
25.4, 25.1 (ppm). 31P NMR (100 MHz, CDCl3) δ = 22.4 (ppm). MS (EI): m/z (%): 91.1 (15), 98.1 (19),
125.0 (100), 127.0 (31), 141.1 (13), 238.1 (97), 239.1 (13), 320.1 (26), 363.2 (20). IR (in KBr): ν =
3184, 2924, 2850, 1444, 1211, 1134, 1047, 998, 857, 763, 559, 523 (cm-1). HRMS (ESI) (m/z) [M +
H+]: Calcd. for C19H24ClNO2P: 364.1233, Found. 364.1228.
P-(2-Bromobenzyloxyl)-N-cyclohexyl-P-phenylphosphonic amide (3ka): White solid (152.3 mg, 75%),
m.p.: 92 - 93 oC. 1H NMR (400 MHz, CDCl3) δ = 7.84 (dd, J = 12.9, 7.6 Hz, 2H), 7.56 – 7.47 (m, 3H),
7.46 – 7.39 (m, 2H), 7.30 (t, J = 7.5 Hz, 1H), 7.15 (t, J = 7.6 Hz, 1H), 5.22 – 5.13 (m, 1H), 5.13 – 5.05
(m, 1H), 3.08 – 2.94 (m, 1H), 2.92 – 2.82 (m, 1H), 1.87 – 1.76 (m, 2H), 1.67 – 1.57 (m, 2H), 1.54 – 1.45
(m, 1H), 1.25 – 1.01 (m, 5H) (ppm). 13C NMR (101 MHz, CDCl3) δ = 136.3 (JC-P = 8.2 Hz), 132.7,
131.9 (JC-P = 2.9 Hz), 131.5 (JC-P = 9.8 Hz), 131.4 (JC-P = 173.3 Hz), 129.5, 129.2, 128.5 (JC-P = 14.3
31
Hz), 127.6, 122.6, 65.4 (JC-P = 4.6 Hz), 50.1, 36.0 (JC-P = 19.0 Hz), 25.4, 25.1 (ppm). P NMR (100
MHz, CDCl3) δ = 22.2 (ppm). MS (EI): m/z = 90.1 (16), 98.1 (13), 169.0 (54), 171.0 (53), 238.1 (51),
246.1 (14), 328.2 (100), 329.2 (21), 364.0 (22), 366.0 (21), 407.1 (2), 409.1 (2). IR (in KBr): ν = 3192,
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2924, 2848, 1443, 1215, 1117, 1051, 1012, 858, 746, 683, 555, 517 (cm-1). HRMS (ESI) (m/z) [M +
H+]: Calcd. for C19H24BrNO2P: 408.0728; Found. 408.0719.
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N-Cyclohexyl-P,P-di-p-tolylphosphinic amide (3la). White solid (165.3 mg, 85%), m.p.: 135 - 136 C.
1H NMR (400 MHz, CDCl3) δ = 7.76 (dd, J = 11.2, 7.9 Hz, 4H), 7.22 (d, J = 7.4 Hz,4H), 3.04 – 2.90
(m, 1H), 2.78 – 2.66 (m, 1H), 2.35 (s, 6H), 2.06 – 1.99 (m, 2H), 1.68 – 1.60 (m, 2H), 1.51 (d, J = 12.1
Hz,1H), 1.26 – 1.06 (m, 5H) (ppm). 13C NMR (100 MHz, CDCl3) δ = 142.1 (JC-P = 2.6 Hz), 132.2 (JC-P
= 9.7 Hz), 130.3 (JC-P = 131.8 Hz), 129.3 (JC-P = 12.9 Hz), 50.5, 36.8 (JC-P = 4.9 Hz), 25.5, 25.2, 21.6
(ppm). 31P NMR (100 MHz, CDCl3) δ = 22.7(ppm). MS (EI): m/z (%): 91.1 (30), 98.1 (44), 229.1 (100),
244.1 (29), 284.1 (45), 327.2 (12).IR(in KBr): ν = 3120, 2929, 2853, 1442, 1189, 1090, 1002, 915, 697,
567, 515 (cm-1).HRMS (ESI) (m/z) [M + H+]: Calcd. for C20H27NOP: 328.1825; Found 328.1828.
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N-cyclohexyl-P,P-di(thiophen-2-yl)phosphinic amide (3ma). White solid (120.1 mg, 78%), m.p.: 156 -
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157 C. H NMR (400 MHz, CDCl3) δ = 7.74 –7.56 (m, 4H), 7.18–7.05 (m, 2H), 3.17– 2.99 (m, 2H),
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2.08– 1.99 (m, 2H),1.71– 1.60 (m, 2H), 1.52 (d, J = 12.1Hz, 1H), 1.26– 1.05 (m, 5H) (ppm). C NMR
(100 MHz, CDCl3) δ = 136.8(JC-P = 11.2 Hz), 134.4 (JC-P = 152.1 Hz), 133.7 (JC-P = 5.8 Hz), 128.4 (JC-P
= 15.6 Hz), 50.9, 36.6 (JC-P = 5.0 Hz), 25.4, 25.2(ppm). 31P NMR (100 MHz, CDCl3) δ = 8.7(ppm). MS
(EI): m/z (%): 83.0 (41), 98.1 (60), 213.0 (100), 228.0 (22), 268.0 (43), 311.1 (11). IR(in KBr): ν =
3142, 2931, 2850, 1442, 1201, 1095, 987, 920, 853, 721, 565 (cm-1). HRMS (ESI) (m/z) [M +
H+]: Calcd. for C14H18NOPS2: 312.0646; Found 312.0641.
N-Cyclohexyl-N-methyl-P,P-diphenylphosphinic amide (3na): White solid (152.3 mg, 75%), m.p.: 92 -
93 oC. 1H NMR (400 MHz, CDCl3) δ = 7.92 – 7.75 (m, 4H), 7.53 – 7.36 (m, 6H), 3.21 – 3.05 (m, 1H),
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2.51 (d, J = 11.4 Hz, 3H), 1.80 – 1.66 (m, 4H), 1.63 – 1.47 (m, 3H), 1.16 – 0.91 (m, 3H) (ppm). C
NMR (100 MHz, CDCl3) δ = 132.6 (JC-P = 128.7 Hz), 132.3 (JC-P = 9.2 Hz), 131.6 (JC-P = 2.6 Hz), 128.5
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(JC-P = 12.4 Hz), 55.2 (JC-P = 2.6 Hz), 31.2 (JC-P = 3.6 Hz), 28.2 (JC-P = 3.6 Hz), 26.0, 25.6 (ppm). P
NMR (100 MHz, CDCl3) δ = 30.8 (ppm). MS (EI): m/z (%): 77.1 (21), 112.2 (65), 201.1 (100), 202.1
(30), 216.1 (20), 218.1 (25), 256.2 (46), 313.2 (15). IR (in KBr): ν = 3192, 2924, 2848, 1566, 1444,
1213, 1124, 1053, 1009, 918, 860, 746, 683, 555, 515 (cm-1). HRMS (ESI) (m/z) [M + H+]: Calcd. for
C19H25NOP: 314.1674; Found. 314.1668.
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N-Cyclohexyl-N,P,P-triphenylphosphinic amide (3oa): White solid (152.3 mg, 75%), m.p.: 92 - 93 C.
1H NMR (400 MHz, CDCl3) δ = 7.88 (dd, J = 11.1, 7.8 Hz, 4H), 7.39 – 7.22 (m, 8H), 7.12 (t, J = 7.4 Hz,
2H), 7.04 (t, J = 7.2 Hz, 1H), 3.51 – 3.36 (m, 1H), 2.09 (d, J = 11.6 Hz, 2H), 1.66 (d, J = 12.6 Hz, 2H),
1.43 (d, J = 12.8 Hz, 1H), 1.31 – 1.06 (m, 4H), 0.90 – 0.73 (m, 1H) (ppm). 13C NMR (100 MHz, CDCl3)
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δ = 139.2 (JC-P = 1.5 Hz), 132.6 (JC-P = 8.7 Hz), 132.6 (JC-P = 5.8 Hz), 132.5 (JC-P = 130.6 Hz), 131.3
(JC-P = 2.7 Hz), 128.2, 128.1 (JC-P = 12.5 Hz), 126.6, 58.1 (JC-P = 3.5 Hz), 33.4 (JC-P = 3.4 Hz), 26.1,
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25.2 (ppm). P NMR (100 MHz, CDCl3) δ = 26.2 (ppm). MS (EI): m/z (%): 77.1 (15), 174.2 (100),
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175.2 (14), 201.1 (57), 202.1 (11), 292.1 (13), 293.1 (14), 332.2 (7), 375.3 (4). IR (in KBr): ν = 3194,
2984, 2855, 1445, 1113, 1075, 997, 918, 854, 750, 692, 547 (cm-1). HRMS (ESI) (m/z) [M + H+]: Calcd.
for C24H27NOP: 376.1830; Found. 376.1834.
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N-Cyclopentyl-P,P-diphenylphosphinic amide (3ab). White solid (123.1 mg, 86%), m.p.: 161 - 162 C.
1H NMR (400 MHz, CDCl3) δ = 7.89 (dd, J = 11.2, 7.8 Hz, 4H), 7.52 – 7.38 (m, 6H), 3.56 – 3.41 (m,
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1H), 2.91 – 2.76 (m, 1H), 2.01 – 1.88 (m, 2H), 1.72 – 1.58 (m, 2H), 1.54 – 1.40 (m, 4H) (ppm). C
NMR (100 MHz, CDCl3) δ = 133.1 (JC-P = 129.2 Hz), 132.3 (JC-P = 9.4 Hz), 131.8 (JC-P = 2.7 Hz), 128.6
(JC-P = 12.5 Hz), 53.4 (JC-P = 1.7 Hz), 35.8 (JC-P = 5.2 Hz), 23.3 (ppm). 31P NMR (100 MHz, CDCl3) δ =
22.2 (ppm). MS (EI): m/z (%): 77.1 (11), 84.1 (72), 142.1 (29), 201.1 (100), 202.1 (40), 216.1 (36),
256.1 (30), 285.1 (11). IR (in KBr): ν = 3178, 2928, 2850, 1448, 1207, 1114, 1049, 753, 687, 555, 514
(cm-1). HRMS (ESI) (m/z) [M + H+]: Calcd. for C17H20NOP: 286.1361; Found. 286.1365.
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N-Cycloheptyl-P,P-diphenylphosphinic amide (3ac). White solid (124.4 mg, 79%), m.p.: 134 - 135 C.
1H NMR (400 MHz, CDCl3) δ = 7.89 (dd, J = 11.6, 7.7 Hz, 4H), 7.54 – 7.34 (m, 6H), 3.29 – 3.13 (m,
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1H), 2.99 – 2.78 (m, 1H), 2.12 – 1.98 (m, 2H), 1.63 – 1.40 (m, 8H), 1.40 – 1.28 (m, 2H) (ppm). C
NMR (100 MHz, CDCl3) δ = 133.2 (JC-P = 129.5 Hz), 132.2 (JC-P = 9.3 Hz), 131.8 (JC-P = 2.6 Hz), 128.6
(JC-P = 12.5 Hz), 52.8 (JC-P = 1.7 Hz), 38.4 (JC-P = 4.9 Hz), 28.2, 23.7 (ppm). 31P NMR (100 MHz,
CDCl3) δ = 21.9 (ppm). MS (EI): m/z (%): 77.1 (18), 112.1 (24), 201.1 (100), 202.1 (34), 216.1 (42),
256.2 (30), 313.2 (12). IR (in KBr): ν = 3184, 2926, 2845, 1448, 1215, 1120, 1059, 854, 746, 683, 555,
515 (cm-1). HRMS (ESI) (m/z) [M + H+]: Calcd. for C19H25NOP: 314.1674; Found. 314.1679.
N-Cyclooctyl-P,P-diphenylphosphinic amide (3ad). White solid (106.4 mg, 65%), m.p.: 106 - 107 oC. 1H
NMR (400 MHz, CDCl3) δ = 7.89 (dd, J = 11.7, 7.7 Hz, 4H), 7.54 – 7.36 (m, 6H), 3.34 – 3.15 (m, 1H),
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2.98 – 2.79 (m, 1H), 2.04 – 1.92 (m, 2H), 1.70 – 1.56 (m, 4H), 1.56 – 1.37 (m, 8H) (ppm). C NMR
(100 MHz, CDCl3) δ = 133.2 (JC-P = 129.5 Hz), 132.2 (JC-P = 9.3 Hz), 131.8 (JC-P = 2.7 Hz), 128.6 (JC-P
= 12.5 Hz), 51.6 (JC-P = 1.8 Hz), 34.9 (JC-P = 4.9 Hz), 27.6, 25.4, 23.4 (ppm). 31P NMR (100 MHz,
CDCl3) δ = 22.0 (ppm). MS (EI): m/z (%): 77.0 (9), 106.1 (9), 126.1 (13), 201.0 (100), 202.0 (32), 218.0
(21), 243.0 (18), 256.1 (46), 327.1 (17). IR (in KBr): ν = 3187, 2930, 2851, 1446, 1213, 1100, 1048,
755, 691, 568, 517 (cm-1). HRMS (ESI) (m/z) [M + H+]: Calcd. for C20H27NOP: 328.1830;
Found. 328.1823.
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N-(Hexan-3-yl)-P,P-diphenylphosphinic amide (3ae) and N-(hexan-2-yl)-P,P-diphenylphosphinic amide
(3ae’): Yellowish thick oil (112.7 mg, 75%). 1H NMR (400 MHz, CDCl3) δ = 7.98 – 7.76 (m, 4H), 7.51
– 7.34 (m, 6H), 3.23 – 3.08 (m, 0.63H), 3.05 – 2.93 (m, 0.34H), 2.77 – 2.66 (m, 1H), 1.62 – 1.16 (m,
8H), 0.91 – 0.78 (m, 4H) (ppm). 13C NMR (100 MHz, CDCl3) δ = 133.23 (JC-P = 129.2 Hz), 132.89 (JC-
P = 124.1 Hz), 132.27 (JC-P = 9.4 Hz), 132.13 (JC-P = 9.5 Hz), 131.78 (JC-P = 2.6 Hz), 131.76 (JC-P = 2.6
Hz), 128.52 (JC-P = 12.5 Hz), 128.49 (JC-P = 12.5 Hz), 52.62 (JC-P = 2.0 Hz), 47.74 (JC-P = 1.7 Hz),
39.52 (JC-P = 6.3 Hz), 38.51 (JC-P = 5.3 Hz), 29.45 (JC-P = 4.6 Hz), 28.16, 23.96 (JC-P = 4.1 Hz), 22.62,
18.83, 14.17, 14.08, 9.68 (ppm). 31P NMR (100 MHz, CDCl3) δ = 21.93, 21.68 (ppm). MS (EI): m/z (%):
77.1 (17), 201.1 (100), 202.1 (18), 244.1 (71), 258.2 (19), 272.2 (18), 286.2 (5), 301.2 (1). IR (in KBr):
ν = 3178, 2920, 2839, 1447, 1217, 1129, 1072, 993, 864, 746, 690, 554 (cm-1). HRMS (ESI) (m/z) [M +
H+]: Calcd. for C18H25NOP: 302.1674; Found. 302.1683.
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N-Methyl-P,P-diphenylphosphinic amide (4a): Yellowish thick oil (101.9 mg, 88%). Rf = 0.2 (n-
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hexane:EtOAc = 1:1). H NMR (400 MHz, CDCl3) δ = 7.93 – 7.82 (m, 4H), 7.51 – 7.38 (m, 6H), 2.90
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(bs, 1H), 2.65 (dd, J = 12.1, 5.3 Hz, 3H) (ppm). C NMR (100 MHz, CDCl3) δ = 132.2 (JC-P = 129.0
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Hz), 132.2 (JC-P = 9.4 Hz), 131.9 (JC-P = 2.0 Hz), 128.7 (JC-P = 12.5 Hz), 26.9 (ppm). P NMR (100
MHz, CDCl3) δ = 25.3 (ppm). MS (EI): m/z (%): 77.1 (21), 154.1 (23), 155.1 (20), 201.1 (36), 202.1
(100), 230.1 (21), 231.1 (23). IR (in KBr): ν = 3192, 3066, 2904, 2819, 1473, 1431, 1180, 1113, 1069,
839, 696, 561, 517 (cm-1). HRMS (ESI) (m/z) [M + H+]: Calcd. for C13H15NOP: 232.0891; Found.
232.0897.
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P-Methoxyl-N-methyl-P-phenylphosphonic amide (4b): Yellowish thick oil (83.6 mg, 90%). H NMR
(400 MHz, CDCl3) δ = 7.78 – 7.68 (m, 2H), 7.50 – 7.35 (m, 3H), 3.70 (d, J = 9.7 Hz, 3H), 3.28 (bs, 1H),
2.55 – 2.46 (m, 3H) (ppm). 13C NMR (100 MHz, CDCl3) δ = 131.8, 131.4 (JC-P = 9.5 Hz), 130.0 (JC-P
=
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173.2 Hz), 128.4 (JC-P = 14.2 Hz), 50.9 (JC-P = 5.0 Hz), 27.1 (ppm). P NMR (100 MHz, CDCl3) δ =
25.8 (ppm). MS (EI): m/z (%): 77.1 (68), 154.1 (44), 141.0 (52), 155.1 (47), 156.1 (100), 184.1 (31),
185.1 (47). IR (in KBr): ν = 3224, 2965, 2927, 1621, 1450, 1372, 1224, 1072, 990, 872, 745, 702, 558
(cm-1). HRMS (ESI) (m/z) [M + H+]: Calcd. for C8H13NO2P: 186.0684; Found. 186.0693.
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P-Ethoxyl-N-methyl-P-phenylphosphonic amide (4c). Yellowish thick oil (83.6 mg, 90%). H NMR
(400 MHz, CDCl3) δ = 7.77 (dd, J = 12.3, 7.5 Hz, 2H), 7.52 – 7.39 (m, 3H), 4.15 – 4.01 (m, 2H), 2.90
(bs, 1H), 2.54 (dd, J = 11.8, 5.8 Hz, 3H), 1.34 (t, J = 7.0 Hz, 3H) (ppm). 13C NMR (100 MHz, CDCl3) δ
= 131.8 (JC-P = 1.8 Hz), 131.4 (JC-P = 9.6 Hz), 130.6 (JC-P = 173.1 Hz), 128.4 (JC-P = 14.2 Hz), 60.4 (JC-P
= 5.7 Hz), 27.2, 16.4 (JC-P = 6.6 Hz) (ppm). 31P NMR (100 MHz, CDCl3) δ = 24.2 (ppm). MS (EI): m/z
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(%): 77.1 (99), 78.1 (100), 94.0 (37), 106.1 (17), 141.0 (88), 142.0 (72), 154.1 (24) 170.1 (48), 171.1
(40), 198.1 (15), 199.1 (25). IR (in KBr): ν = 3215, 2970, 2939, 1653, 1443, 1378, 1210, 1114, 1007,
854, 763, 692, 558, 524 (cm-1). HRMS (ESI) (m/z) [M + H+]: Calcd. for C9H15NO2P: 200.0840; Found.
200.0846.
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P-Isopropoxyl-N-methyl-P-phenylphosphonic amide (4d). Yellowish thick oil (91.7 mg, 86%). 1H NMR
(400 MHz, CDCl3) δ = 7.74 (dd, J = 12.1, 7.8 Hz, 2H), 7.48 – 7.35 (m, 3H), 4.78 – 4.63 (m, 1H), 3.09
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(bs, 1H), 2.49 (dd, J = 11.9, 5.6 Hz, 3H), 1.33 (d, J = 6.1 Hz, 3H), 1.28 (d, J = 6.1 Hz, 3H) (ppm). C
NMR (100 MHz, CDCl3) δ = 131.6 (JC-P = 2.8 Hz), 131.4 (JC-P = 9.6 Hz), 131.1 (JC-P = 173.0 Hz), 128.3
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(JC-P = 14.1 Hz), 69.1 (JC-P = 5.7 Hz), 27.2, 24.2 (JC-P = 4.1 Hz), 24.1 (JC-P = 4.4 Hz) (ppm). P NMR
(100 MHz, CDCl3) δ = 23.1 (ppm). MS (EI): m/z (%): 77.1 (54), 78.1 (47), 94.0 (9), 106.1 (17), 141.0
(34), 142.0 (68), 154.1 (53) 155.1 (34), 172.1 (100), 213.1 (11). IR (in KBr): ν = 3236, 2980, 2931,
1649, 1439, 1381, 1217, 1128, 995, 893, 845, 750, 702, 559 (cm-1). HRMS (ESI) (m/z) [M +
H+]: Calcd. for C10H17NO2P: 214.0997; Found. 214.0989.
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P-Butoxyl- N-methyl-P-phenylphosphonic amide (4e). Yellowish thick oil (104.7 mg, 92%). H NMR
(400 MHz, CDCl3) δ = 7.77 (dd, J = 12.3, 7.7 Hz, 2H), 7.52 – 7.46 (m, 1H), 7.46 – 7.39 (m, 2H), 4.07 –
3.98 (m, 2H), 2.87 (bs, 1H), 2.54 (dd, J = 11.7, 5.4 Hz, 3H), 1.71 – 1.62 (m, 2H), 1.47 – 1.35 (m, 2H),
0.92 (t, J = 7.3 Hz, 3H) (ppm). 13C NMR (100 MHz, CDCl3) δ = 131.7 (JC-P = 1.7 Hz), 131.4 (JC-P = 9.5
Hz), 130.6 (JC-P = 173.4 Hz), 128.4 (JC-P = 14.2 Hz), 64.1 (JC-P = 5.5 Hz), 32.6 (JC-P = 6.7 Hz), 27.2,
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19.0, 13.7 (ppm). P NMR (100 MHz, CDCl3) δ = 24.1 (ppm). MS (EI): m/z (%): 77.1 (74), 78.1 (36),
91.1 (20), 105.1 (16), 123.0 (20), 141.0 (48), 142.0 (27), 154.1 (36), 172.1 (100), 199.0 (30), 216.0 (50),
227.1 (4). IR (in KBr): ν = 3201, 2957, 2917, 1655, 1445, 1223, 1008, 885, 845, 776, 695, 563 (cm-1).
HRMS (ESI) (m/z) [M + H+]: Calcd. C11H18NO2P 228.1153, Found. 228.1161.
P-(2-Methoxyethoxyl)-N-methyl-P-phenylphosphonic amide (4f). Yellowish thick oil (91.6 mg, 80%). Rf
= 0.1 (n-hexane:EtOAc = 1:1). 1H NMR (400 MHz, CDCl3) δ = 7.80 (dd, J = 12.8, 7.6 Hz, 2H), 7.54 –
7.48 (m, 1H), 7.47 – 7.40 (m, 2H), 4.27 – 4.09 (m, 2H), 3.62 (t, J = 4.3 Hz, 2H), 3.37 (s, 3H), 2.99 –
2.83 (m, 1H), 2.57 (dd, J = 11.8, 5.7 Hz, 3H) (ppm). 13C NMR (101 MHz, CDCl3) δ = 132.0 (JC-P = 2.9
Hz), 131.7 (JC-P = 9.8 Hz), 130.3 (JC-P = 173.9 Hz), 128.5 (JC-P = 14.3 Hz), 72.0 (JC-P = 6.3 Hz), 63.5
(JC-P = 5.8 Hz), 59.1, 27.2 (ppm). 31P NMR (100 MHz, CDCl3) δ = 24.9 (ppm). MS (EI): m/z (%): 58.0
(16), 77.0 (15), 107.1 (5), 142.0 (14), 154.1 (69), 172.1 (100), 186.1(5), 199.1 (10), 229.1 (2). IR (in
KBr): ν = 3197, 2935, 2852, 1453, 1213, 1134, 1041, 924, 823, 754, 701, 562, 533 (cm-1).
HRMS (ESI) (m/z) [M + H+]: Calcd. for C10H17NO3P: 230.0946; Found. 230.0954.
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P-(3-Chloropropoxyl)-N-methyl-P-phenylphosphonic amide (4g). Yellowish thick oil (101.3 mg, 82%).
1H NMR (400 MHz, CDCl3) δ = 7.76 (dd, J = 12.8, 7.3 Hz, 2H), 7.54 – 7.40 (m, 3H), 4.23 – 4.12 (m,
2H), 3.67 (t, J = 6.2 Hz, 2H), 3.12 – 2.90 (m, 1H), 2.55 (dd, J = 11.8, 5.5 Hz, 3H), 2.20 – 2.10 (m, 2H)
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(ppm). 13C NMR (100 MHz, CDCl3) δ = 132.0 (JC-P = 2.8 Hz), 131.4 (JC-P = 9.7 Hz), 130.1 (JC-P
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173.5 Hz), 128.6 (JC-P = 14.2 Hz), 60.9 (JC-P = 5.5 Hz), 41.1, 33.4 (JC-P = 6.7 Hz), 27.2 (ppm). 31P NMR
(100 MHz, CDCl3) δ = 24.6 (ppm). MS (EI): m/z (%): 77.0 (72), 105.0 (56), 141.0 (38), 154.1 (86),
172.1 (40), 183.1 (23), 212.1 (100), 248.1 (2). IR (in KBr): ν = 3212, 2933, 2854, 1602, 1439, 1218,
1109, 1028, 983, 920, 739, 555 (cm-1). HRMS (ESI) (m/z) [M + H+]: Calcd. for C10H15ClNO2P:
248.0607; Found. 248.0617.
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P-Benzyloxyl-N-methyl-P-phenylphosphonic amide (4h). Yellowish thick oil (106.7 mg, 82%). 1H NMR
(400 MHz, CDCl3) δ = 7.79 (dd, J = 12.8, 7.4 Hz, 2H), 7.53 – 7.28 (m, 8H), 5.14 – 5.03 (m, 2H), 3.11
(bs, 1H), 2.51 (dd, J = 11.9, 5.7 Hz, 3H) (ppm). 13C NMR (101 MHz, CDCl3) δ = 136.8 (JC-P = 7.2 Hz),
132.0 (JC-P = 2.9 Hz), 131.5 (JC-P = 9.7 Hz), 130.2 (JC-P = 173.3 Hz), 128.6, 128.5 (JC-P = 14.4 Hz),
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128.3, 127.8, 65.8 (JC-P = 5.3 Hz), 27.2 (ppm). P NMR (100 MHz, CDCl3) δ = 25.0 (ppm). MS (EI):
m/z (%): 65.1 (27), 77.1 (25), 78.1 (61), 91.1 (100), 141.0 (12), 155.1 (82), 167.1 (21), 261.1 (35). IR (in
KBr): ν = 3168, 2930, 2854, 1600, 1455, 1203, 1132, 1035, 924, 856, 784, 745, 689 (cm-1).
HRMS (ESI) (m/z) [M + H+]: Calcd. for C14H17NO2P: 262.0997; Found. 262.1004.
P-(3-Fluorobenzyloxyl)-N-methyl-P-phenylphosphonic amide (4i). Yellowish thick oil (106.7 mg, 82%).
1H NMR (400 MHz, CDCl3) δ = 7.73 (dd, J = 12.6, 7.8 Hz, 2H), 7.48 – 7.41 (m, 1H), 7.40 – 7.32 (m,
2H), 7.23 (q, J = 7.4 Hz, 1H), 7.06 (dd, J = 12.9, 9.5 Hz, 2H), 6.92 (t, J = 8.1 Hz, 1H), 4.99 (d, J = 7.2
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Hz, 2H), 3.24 (bs, 1H), 2.45 (dd, J = 11.7, 5.5 Hz, 3H) (ppm). C NMR (101 MHz, CDCl3) δ = 162.9
(JC-F = 246.2 Hz), 139.3 (JC-P = 7.3 Hz), 132.1 (JC-P = 2.9 Hz), 131.5 (JC-P = 9.8 Hz), 130.2 (JC-P = 8.2
Hz), 129.9 (JC-P = 173.3 Hz), 128.6 (JC-P = 14.3 Hz), 123.1 (JC-P = 2.9 Hz), 115.1 (JC-P = 21.1 Hz), 114.5
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(JC-P = 22.1 Hz), 64.9 (JC-P = 5.0 Hz), 27.2 (ppm). F NMR (375 MHz, CDCl3) δ = -112.7 (ppm). P
NMR (100 MHz, CDCl3) δ = 25.3 (ppm). MS (EI): m/z (%): 77.1 (25), 78.1 (66), 83.0 (25), 109.1 (100),
155.1 (85), 185.1 (14), 279.1 (42). IR (in KBr): ν = 3167, 2934, 2847, 1597, 1459, 1209, 1140, 1038,
924, 852, 790, 748, 684 (cm-1). HRMS (ESI) (m/z) [M + H+]: Calcd. for C14H15FNO2P 280.0903,
Found. 280.0907.
P-(4-Chlorobenzyloxyl)-N-methyl-P-phenylphosphonic amide (4j). Yellowish thick oil (106.6 mg,
72%). 1H NMR (400 MHz, CDCl3) δ = 7.78 (dd, J = 12.3, 7.8 Hz, 2H), 7.53 – 7.47 (m, 1H), 7.46 – 7.39
(m, 2H), 7.31 (bs, 4H), 5.03 (d, J = 7.4 Hz, 2H), 3.14 (bs, 1H), 2.51 (dd, J = 11.3, 5.1 Hz, 3H) (ppm).
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13C NMR (100 MHz, CDCl3) δ = 135.3 (JC-P = 7.0 Hz), 134.1, 132.1 (JC-P = 2.8 Hz), 131.5 (JC-P = 9.8
Hz), 130.0 (JC-P = 173.2 Hz), 129.2, 128.8, 128.6 (JC-P = 14.3 Hz), 65.0 (JC-P = 5.2 Hz), 27.2 (ppm). 31P
NMR (100 MHz, CDCl3) δ = 25.2 (ppm). MS (EI): m/z (%): 77.0 (18), 78.0 (59), 89.0 (21), 125.0 (72),
127.0 (24), 155.1 (100), 295.0 (42), 297.0 (14). IR (in KBr): ν = 3172, 2931, 2850, 1593, 1460, 1207,
1132, 1037, 922, 852, 789, 746, 687 (cm-1). HRMS (ESI) (m/z) [M + H+]: Calcd. for C14H16ClNO2P:
296.0607, Found. 296.0601.
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P-(2-Bromobenzyl)oxyl- N-methyl-P-phenylphosphonic amide (4k): Yellowish thick oil (113.6 mg,
67%). 1H NMR (400 MHz, CDCl3) δ = 7.83 (dd, J = 12.9, 7.1 Hz, 2H), 7.58 – 7.48 (m, 3H), 7.48 – 7.40
(m, 2H), 7.31 (t, J = 7.4 Hz, 1H), 7.17 (t, J = 7.4 Hz, 1H), 5.24 – 5.10 (m, 2H), 3.12 (bs, 1H), 2.55 (dd, J
= 12.0, 5.9 Hz, 3H) (ppm). 13C NMR (101 MHz, CDCl3) δ = 136.2 (JC-P = 7.9 Hz), 132.7, 132.1 (JC-P
=
3.0 Hz), 131.5 (JC-P = 9.8 Hz), 130.0 (JC-P = 173.9 Hz), 129.6, 129.4, 128.6 (JC-P = 14.3 Hz), 127.7,
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122.7, 65.27 (JC-P = 4.9 Hz), 27.3 (ppm). P NMR (100 MHz, CDCl3) δ = 25.0 (ppm). MS (EI): m/z =
77.1 (11), 78.1 (22), 89.1 (14), 90.1 (20), 154.1 (22), 155.1 (17), 169.0 (20), 171.0 (19), 229.1 (11),
260.1 (100), 261.1 (16), 339.0 (1), 341.0 (1). IR (in KBr): ν = 3183, 2924, 2853, 1595, 1452, 1216,
1122, 1040, 857, 746, 689, 557 (cm-1). HRMS (ESI) (m/z) [M + H+]: Calcd. for C14H16BrNO2P:
340.0102; Found. 340.0110.
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N-methyl-P,P-di-p-tolylphosphinic amide (4l). Yellowish thick oil (113.8 mg, 88%). H NMR (400
MHz, CDCl3) δ = 7.78 –7.69 (m, 4H), 7.22 (d, J = 6.9 Hz,4H), 2.85 (bs, 1H), 2.63 (dd, J = 11.8, 4.6 Hz,
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3H), 2.34 (s, 6H)(ppm). C NMR (100 MHz, CDCl3) δ = 142.3(JC-P = 1.8 Hz), 132.2 (JC-P = 9.6 Hz),
129.4 (JC-P = 12.8 Hz), 129.1 (JC-P = 131.6 Hz), 26.8, 21.6 (ppm). 31P NMR (100 MHz, CDCl3) δ =
22.7(ppm). MS (EI): m/z (%): 91.1 (25), 168.1 (32), 229.1 (100), 230.1 (28), 259.1 (20). IR (in KBr): ν
= 3187, 2910, 2821, 1441, 1182, 1109, 845, 695, 568, 517 (cm-1). HRMS (ESI) (m/z) [M + H+]: Calcd.
for C15H19NOP: 260.1204; Found 260.1201.
N-methyl-P,P-di(thiophen-2-yl)phosphinic amide (4m). Yellowish thick oil (95.2 mg, 78%). Rf = 0.1 (n-
1
hexane:EtOAc = 1:1). H NMR (400 MHz, CDCl3) δ = 7.72–7.55 (m, 4H), 7.15–7.03 (m, 2H), 3.48–
13
3.24 (m, 1H), 2.72–2.53 (m, 3H) (ppm). C NMR (100 MHz, CDCl3) δ = 136.9(JC-P = 11.1 Hz), 133.9
(JC-P = 5.7 Hz), 133.2 (JC-P = 152.2 Hz), 128.4 (JC-P = 15.6 Hz), 27.0(ppm). 31P NMR (100 MHz,
CDCl3) δ = 12.3(ppm). MS (EI): m/z (%): 83.0 (34), 160.0 (22), 213.0 (100), 214.0 (25), 243.0 (21).
IR(in KBr): ν = 3162, 2907, 2825, 1403, 1225, 1180, 1108, 1029, 931, 851, 705, 661 (cm-1).
HRMS (ESI) (m/z) [M + H+]: Calcd. for C9H10NOPS2: 244.0020; Found 244.0026.
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P-Cyclohexyloxyl-N-methyl-P-phenylphosphonic amide (4p). Yellowish thick oil (101.6 mg, 80%). H
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NMR (400 MHz, CDCl3) δ = 7.74 (dd, J = 12.3, 7.8 Hz, 2H), 7.47 – 7.34 (m, 3H), 4.49 – 4.36 (m, 1H),
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3.11 (bs, 1H), 2.48 (dd, J = 11.7, 5.2 Hz, 3H), 1.99 – 1.82 (m, 2H), 1.76 – 1.62 (m, 2H), 1.59 – 1.40 (m,
13
3H), 1.37 – 1.14 (m, 3H) (ppm). C NMR (100 MHz, CDCl3) δ = 131.5 (JC-P = 2.6 Hz), 131.4 (JC-P
=
9.6 Hz), 131.3 (JC-P = 173.3 Hz), 128.3 (JC-P = 14.1 Hz), 73.9 (JC-P = 5.7 Hz), 33.9 (JC-P = 4.0 Hz), 27.2,
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25.2, 23.7 (JC-P = 8.2 Hz) (ppm). P NMR (100 MHz, CDCl3) δ = 23.0 (ppm). MS (EI): m/z = 77.1
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(12), 78.1 (7), 105.1 (20), 105.1 (3), 122.1 (4), 141.0 (6), 142.0 (7), 154.1 (16), 172.1 (100), 173.1 (8),
186.1 (3), 253.1 (1). IR (in KBr): ν = 3209, 2952, 2844, 1451, 1376, 1205, 1133, 976, 829, 748, 693,
555 (cm-1). HRMS (ESI) (m/z) [M + H+]: Calcd. for C13H21NO2P: 254.1310; Found. 254.1320.
P-Cyclohexylmethoxyl-N-methyl-P-phenylphosphonic amide (4q). Yellowish thick oil (101.9 mg, 76%).
1H NMR (400 MHz, CDCl3) δ = 7.78 (dd, J = 12.6, 7.3 Hz, 2H), 7.54 – 7.48 (m, 1H), 7.48 – 7.41 (m,
2H), 3.89 – 3.77 (m, 2H), 2.68 (bs, 1H), 2.55 (dd, J = 11.7, 5.6 Hz, 3H), 1.88 – 1.63 (m, 6H), 1.31 –
1.12 (m, 3H), 1.05 – 0.93 (m, 2H) (ppm). 13C NMR (100 MHz, CDCl3) δ = 131.8 (JC-P = 2.9 Hz), 131.5
(JC-P = 9.5 Hz), 130.6 (JC-P = 173.1 Hz), 128.5 (JC-P = 14.1 Hz), 69.4 (JC-P = 6.1 Hz), 38.6 (JC-P = 6.8
Hz), 29.6 (JC-P = 5.7 Hz), 27.3, 26.5, 25.8 (ppm). 31P NMR (100 MHz, CDCl3) δ = 23.8 (ppm). MS (EI):
m/z (%): 77.1 (14), 91.1 (8), 105.1 (20), 105.1 (6), 141.0 (17), 142.0 (7), 159.0 (100), 172.1 (23), 184.1
(3), 221.1 (3). IR (in KBr): ν = 3214, 2985, 2901, 1650, 1444, 1215, 1119, 1003, 898, 852, 752, 695,
554 (cm-1). HRMS (ESI) (m/z) [M + H+]: Calcd. for C14H23NO2P: 268.1466; Found 268.1459.
Supporting Information:
1H and 13C NMR spectra of all the compounds are available free of charge via the Internet at
http://pubs.acs.org.
AKKNOWLEDGEMENT
We are grateful to the Natural Science Foundation of Hunan Province (No. 2017JJ3027), the
Fundamental Research Funds for Hunan University (No. 531107040840).
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2017, 53, 142 and the citations therein.
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