Organophosphorus-selenium heteroatom derivatives from selenation of primary/secondary amines and haloalkanes/dihaloalkanes

Article abstract of DOI:10.1002/ejoc.201300860

Reaction of 2,4-bis(phenyl)-1,3-diselenadiphosphetane-2,4-diselenide (Woollins' reagent) with four equivalents of primary/secondary amines led to a series of ammonium phenylphosphonamido-diselenoates or phenylphosphonamido- diselenoic diamides 1a-n, the l

Full text of DOI:10.1002/ejoc.201300860

Job/Unit: O30860
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Date: 23-09-13 17:45:29
Pages: 10
FULL PAPER
DOI: 10.1002/ejoc.201300860
Organophosphorus-Selenium Heteroatom Derivatives from Selenation of
Primary/Secondary Amines and Haloalkanes/Dihaloalkanes
Guoxiong Hua,[a] Kasun S. A. Arachchige,[a] Alexandra M. Z. Slawin,[a] and
J. Derek Woollins*[a]
Keywords: Woollins’ reagent / Selenium / Phosphorus / Amines / Haloalkanes
Reaction of 2,4-bis(phenyl)-1,3-diselenadiphosphetane-2,4-
diselenide (Woollins’ reagent) with four equivalents of pri-
mary/secondary amines led to a series of ammonium phenyl-
phosphonamido-diselenoates or phenylphosphonamido-di-
selenoic diamides 1a–n, the latter further reacted in situ with
either two equivalents of haloalkanes or an equimolar
amount of dihaloalkane, resulting in formation of the corre-
sponding Se-alkylphenyl-Se-alkylphenyl-phosphonamidodi-
selenoates 2a–n and alkane bis(N-alkyl-P-phenylphosphon-
amido-diselenoate) derivatives 3a–n in good to excellent
yields. All new compounds have been characterized spectro-
scopically including multinuclear NMR (1H, 13C, 31P and
77Se), IR and mass spectroscopy. Two representative X-ray
structures are also described.
phonamido-diselenoate) derivatives through the reaction of
WR with primary/secondary amines, followed by treatment
with haloalkanes or dihaloalkanes in situ. We also report
two representative X-ray structures.
Introduction
Organophosphorus chemistry has attracted huge atten-
tion in both academic and industrial research for several
decades.[1–3] A wide range of applications have been docu-
mented in fields such as coordination chemistry, material
science, homogeneous catalysis, the synthesis of biologically
active agents or pesticides, and additives for polymers such
as lubricants and antioxidants.[4–10] 2,4-Bis(phenyl)-1,3-
diselenadiphosphethane-2,4-diselenide [{PhP(Se)(μ-Se)}2]
(Woollins’ reagent, WR), a selenium counterpart of the
well-known Lawesson’s reagent (LR), has been well-devel-
oped in recent years as an efficient phosphorus-selenium-
containing building block or selenation reagent for organic
synthetic chemistry.[11] The reactions of WR with various
organic substrates ranges from simple oxygen–selenium ex-
change to the formation of complex phosphorus-selenium
heterocycles as well as the formation of surprising phos-
phorus-selenium-free products.[12–25] We have recently re-
ported the synthesis of a series of ammonium phenylphos-
phonamido-diselenoates and phenylphosphonamido-di-
selenoic diamides from the reaction of WR with primary
or secondary amines,[26] and the formation of a series of
organophosphorus-selenium heteroatom derivatives from
the selenation of alkenyl or arynyl-diamines.[27] As a part of
our continuing exploration into the reactivity of WR
towards different organic nucleophiles, herein, we report the
synthesis of a series of novel Se-alkylphenylphosphon-
amido-diselenoate and alkane bis(N-alkyl-P-phenylphos-
Results and Discussion
Treatment of WR with four molar equivalents of primary
or secondary amine in anhydrous tetrahydrofuran (THF) at
ambient temperature for 2 h proceeded with cleavage of the
four-membered ring in WR, leading to formation of the
corresponding ammonium salts of phenylphosphonamido-
diselenoates and phenylphosphonamido-diselenoic di-
amides 1a–n in almost quantitative yields.[26] These ammo-
nium salts were further reacted in situ with two equivalents
of haloalkanes at ambient temperature for 24 h to give the
corresponding Se-alkylphenylphosphonamido-diselenoates
2a–n, as depicted in Scheme 1. These new heteroatom com-
pounds were isolated in good to excellent yields (41–93%;
Table 1) as either sticky oils or pastes that were soluble in
both chlorinated solvents and tetrahydrofuran. It should be
noted that products 2e–l, bearing a strong electron-with-
drawing group R3 (p-BrC6H4COCH2), were obtained in
rather high yields (55–93%), whereas products 2b and 2c,
bearing a less electron-withdrawing group R3 [CH3(CH2)10
or CH3(CH2)6], were isolated in the lowest yields (41 and
42%, respectively). Thus, it appears that a strong electron-
withdrawing group R3 is hugely beneficial for the formation
of the reaction products. Compounds 2a–n are stable to air
and moisture for months without any clear signs of degra-
dation.
[a] EaStCHEM School of Chemistry, University of St Andrews,
St Andrews, Fife, Scotland, KY16 9ST, UK
E-mail: jdw3@st-and.ac.uk
http://www.st-andrews.ac.uk/chemistry/
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201300860.
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G. Hua, K. S. A. Arachchige, A. M. Z. Slawin, J. D. Woollins
Table 1. Se-Alkylphenylphosphonamidodiselenoates 2a–n and their 31P and 77Se NMR spectra.
FULL PAPER
X
R1
R2
R3
Product
Yield
(%)
δP (ppm)
[(JP,Se), Hz]
δSe (ppm)
[(JP,Se), Hz]
Cl
Br
Br
Br
Br
Br
c-Hexyl
c-Hexyl
c-Hexyl
c-Hexyl
tBu
H
H
H
H
H
H
C6H5COCH2
CH3(CH2)10
2a
2b
2c
54
42
41
59
82
93
53.7 [371/792]
53.2 [391/786]
53.2 [390/786]
53.2 [390/786]
46.9 [355/794]
345.4 [371]
–102.0 [792]
323.6 [391]
–104.5 [786]
323.6 [390]
–104.6 [786]
323.6 [391]
–104.4 [786]
384.0 [355]
–53.0 [792]
346.1 [367]
–101.9 [794]
348.5 [374]
–104.8 [784]
321.2 [370]
–100.4 [794]
347.7 [369]
–100.7 [794]
338.8 [369]
–95.3 [791]
345.3 [370]
–102.4 [794]
311.7 [367]
–26.1 [789]
299.8 [362]
–93.5 [799]
361.4 [388]
–26.4 [777]
324.8 [376]
–103.4 [798]
CH3(CH2)8
CH3(CH2)6
2d
2e
1,4-BrC6H4COCH2
1,4-BrC6H4COCH2
sBu
2f[a]
56.0 [366/796]
54.8 [373/782]
Br
Br
Br
Br
Br
Br
Br
Br
nBu
c-Hexyl
c-Pentyl
iPr
H
1,4-BrC6H4COCH2
1,4-BrC6H4COCH2
1,4-BrC6H4COCH2
1,4-BrC6H4COCH2
1,4-BrC6H4COCH2
1,4-BrC6H4COCH2
2g
2h
2i
81
56
81
88
55
67
44
47
58.0 [370/794]
54.5 [369/794]
55.8 [369/791]
54.6 [369/794]
62.5 [366/789]
78.4 [362/798]
59.9 [387/777]
58.3 [376/798]
H
H
H
2j
iPr
iPr
iBu
iPr
H
2k
2l
iBu
iPr
1,2-(HOCH2)C6H4CH2 2m
1,4-BrC6H4COCH2 2n
Bn
[a] Two diastereomers were found in compound 2f.
from P=Se in the range of δ = –104.8 to –26.1 ppm, respec-
tively, with matching 31P–77Se coupling constants (Table 1).
The molecular structures of 2e and 2i were confirmed by
single-crystal X-ray diffraction analysis, which are shown
in Figure 1[28] and Figure 2.[29] The transparent, colourless
cubic crystals of 2e and 2i were grown from dichlorometh-
ane solution with slow diffusion of hexane. Compound 2e
¯
crystallized in the triclinic space group P1, whereas com-
pound 2i crystallized in the monoclinic space group P21/c
with two independent molecules per unit cell. In compound
Scheme 1. Synthesis of Se-alkylphenylphosphonamidodiselenoates
2a–n (R groups defined in Table 1).
1
Compounds 2a–n were characterised by IR and H, 13C,
31P and 77Se NMR spectroscopy and by mass spectrometry.
All new compounds showed the anticipated [M + H]+ or
[M + Na]+ peak in their mass spectra and satisfactory accu-
rate mass measurements. Two isomers were found in the
NMR spectra of 2f. The 31P NMR spectra of 2a–n display
sharp singlets in the range of 46.9–78.4 ppm, flanked by
two pairs of selenium satellites with 31P–77Se coupling con-
stants in the range of 355–391 Hz and 777–798 Hz, indicat-
ing the presence of P–Se single bonds and P=Se double
bonds in each compound. This was further substantiated
by the 77Se NMR spectra of 2a–n, which contain signals
Figure 1. X-ray structure of 2e (hydrogen atoms omitted for clar-
ity). Selected bond lengths [Å] and angles (°) (esds in parentheses):
Se(1)–P(1) 2.103(3), Se(2)–P(1) 2.257(3), Se(2)–C(11) 1.948(9),
P(1)–C(1) 1.807(8), P(1)–N(1) 1.666(6), N(1)–C(7) 1.488(9); P(1)–
Se(2)–C(11) 99.3(3), Se(1)–P(1)–Se(2) 113.48(11), Se(1)–P(1)–N(1)
120.7(2), Se(1)–P(1)–C(1) 113.0(3), Se(2)–P(1)–N(1) 100.8(3),
Se(2)–P(1)–C(1) 100.4(3), N(1)–P(1)–C(1) 106.0(4), P(1)–N(1)–C(7)
arising from SeR in the range of δ = 299.8–384.0 ppm and 124.9(5).
2
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Organophosphorus-Selenium Heteroatom Derivatives
and P(1)–Se(2) [2.281(4)/2.208(4) Å] bond lengths in 2i are
consistent with P–Se single bonds (2.2–2.3 Å) and P=Se
double bonds (2.08–2.12 Å) in similar compounds.[25,30,31]
We also carried out analogous reactions by using di-
haloalkanes instead of monohaloalkanes. Thus, ammonium
phenyldiselenophosphonates 1a–n were further reacted in
situ with one molar equivalent of dibromoalkanes in tetra-
hydrofuran at ambient temperature for 24 h to give the cor-
responding Se-alkylphenylphosphonamido-diselenoates 3a–
n, as shown in Scheme 2. These new compounds were iso-
lated in moderate to good yields (51–80%; Table 2) as sticky
Figure 2. X-ray structure of 2i (hydrogen atoms omitted for clarity).
Selected bond lengths [Å] and angles (°) (esds in parentheses) (di-
mensions for second independent molecule in square parentheses):
Se(1)–P(1) 2.097(4) [2.103(4)], Se(2)–P(1) 2.281(4) [2.208(4)], Se(2)–
C(12) 1.950(11) [1.972(10)], P(1)–C(1) 1.791(10) [1.838(10)], P(1)–
N(1) 1.666(6) [1.644(9)], N(1)–C(7) 1.483(12) [1.513(12)]; P(1)–
Se(2)–C(11) 99.4(3) [101.3(3)], Se(1)–P(1)–Se(2) 114.09(12)
[114.29(12)], Se(1)–P(1)–N(1) 113.3(3) [111.2(4)], Se(1)–P(1)–C(1)
113.7(4) [113.3(4)], Se(2)–P(1)–N(1) 109.4(3) [110.1(3)], Se(2)–P(1)–
C(1) 101.3(4) [100.6(4)], N(1)–P(1)–C(1) 106.4(5) [106.6(5)], P(1)–
N(1)–C(7) 119.2(6) [121.1(7)].
2e, the two phenyl rings are inclined 56.85° to one another.
The P(1)–Se(1) [2.103(3) Å] and P(1)–Se(2) [2.0954(13) Å]
Scheme 2. Synthesis of Se-alkylphenylphosphonamidodiselenoates
bond lengths in 2e and the P(1)–Se(1) [2.097(4)/2.103(4)] 3a–n (R and E groups are defined in Table 2).
Table 2. Se-Alkylphenylphosphonamidodiselenoates 3a–n and their 31P and 77Se NMR spectra.
Product
R1
R2
H
E
Yield (%)
79
δP (ppm) [(JP,Se), Hz]
δSe (ppm) [(JP,Se), Hz]
3a
c-Hexyl
CH2
54.9 [374/791]
54.8 [371/791]
52.5 [384/789]
52.4 [386/786]
53.7 [384/789]
53.6 [386/786]
53.5 [384/789]
53.4 [386/786]
53.9 [386/789]
53.8 [386/789]
53.0 [383/786]
52.7 [385/784]
53.9 [385/789]
53.8 [385/789]
54.2 [385/786]
54.1 [385/786]
77.1 [386/792]
76.8 [386/794]
76.2 [386/794]
76.1 [386/792]
54.0 [387/789]
53.9 [387/789]
46.1 [374/794]
45.9 [367/789]
45.8 [377/789]
46.0 [376/789]
45.9 [378/786]
55.2 [384/789]
55.1 [384/789]
54.8 [384/789]
54.7 [387/789]
55.0 [390/789]
54.9 [390/789]
54.6 [390/789]
54.5 [390/789]
398.6 [371], –91.9 [791]
395.5 [374], –92.7 [791]
378.5 [384], –90.1 [784]
375.6 [386], –94.7 [786]
325.1 [384], –102.8 [789]
324.8 [386], –103.5 [786]
326.7 [386], –105.0[789]
326.3 [388], –105.2 [786]
395.9 [386], –96.7 [789]
395.1 [386], –96.8 [789]
514.7 [385], –248.5 [784]
514.5 [383], –248.7 [786]
323.4 [385], –164.2 [789]
323.0 [385], –173.8 [789]
392.7 [385], –99.5 [786]
392.1 [385], –99.7 [786]
357.1 [386], –95.6 [792]
354.1 [386], –96.7 [794]
350.5 [386], –98.4 [794]
350.1 [386], –99.1 [792]
408.5 [386], –99.1 [789]
408.4 [385], –99.3 [789]
450.7 [374], –49.2 [789]
447.8 [377], –49.8 [789]
447.2 [367], –50.4 [789]
438.8 [378], –50.3 [789]
438.1 [385], –50.4 [789]
395.9 [384], –99.0 [789]
395.2 [384], –99.5 [789]
394.8 [384], –101.2 [789]
391.4 [387], –101.4 [789]
406.4 [390], –97.1 [789]
406.2 [390], –97.5 [789]
406.1 [390], –99.1 [789]
405.7 [390], –99.5 [789]
3b
3c
3d
3e
3f
c-Hexyl
c-Hexyl
c-Hexyl
c-Hexyl
iPr
H
H
H
H
H
H
H
CH2CH2
80
70
78
77
65
55
56
53
CH2CH2CH2
CH2CH2CH2CH2
1,2-CH2C6H4CH2
CH2CH2
3g
3h
3i
iPr
CH2CH2CH2
1,2-CH2C6H4CH2
iPr
iBu
iBu 1,2-CH2C6H4CH2
3j
iPr
H
H
biphenyl-4,4Ј-diylbis(methylene)
54
59
3k
tBu
1,3-CH2C6H4CH2
3l
tBu
sBu
H
H
1,2-CH2C6H4CH2
1,2-CH2C6H4CH2
51
54
3m
3n
sBu
H
1,3-CH2C6H4CH2
60
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G. Hua, K. S. A. Arachchige, A. M. Z. Slawin, J. D. Woollins
FULL PAPER
oils, pastes or solids that were soluble in chloroform, phosphonamido-diselenoic diamides, which were derived
dichloromethane and tetrahydrofuran, and insoluble in di- from the reaction of WR with primary/secondary amines,
ethyl ether and hexane.
with either two molar equivalents of haloalkanes or one
The characterisation of 3a–n was made on the basis of molar equivalent of dibromoalkanes. All new compounds
1H, 13C, 31P and 77Se NMR, IR spectroscopy and mass were fully characterised by means of IR, mass spectroscopy
spectrometry. All new compounds showed the anticipated and multinuclear NMR analysis in conjunction with single-
[M + H]+ or [M + Na]+ peak in their mass spectra and crystal X-ray crystallography of two structures.
satisfactory accurate mass measurements were obtained for
all compounds. The 31P NMR spectra of 3a–h, 3j and 3l
Experimental Section
exhibit two sets of double resonances (as a consequence of
the stereoisomers present) with two sets of satellites,
whereas, interestingly, the 31P NMR spectra of 3i, 3m and
3n displayed four sets of double resonances, and three sets
of double resonances were found in 3k, as a consequence
of the stereoisomers present (Table 2). The two phosphorus
atoms constitute potential stereogenic centres in com-
pounds 3a–n, thus, stereotopic (R,R), (S,S), (S,R) and (R,S)
stereoisomers are possible. Not surprisingly, in the 31P
NMR spectra of 3a–h, 3j and 3l, two phosphorus signals
with different intensity ratio (see experimental section) were
observed in the range δ = 52.4–54.9 ppm, flanked by two
sets of satellites for the endocyclic and exocyclic selenium
atoms [J(P,Seendo) coupling constants being in the range of
371–387 Hz and J(P,Seexo) coupling constants in the range
of 784–794 Hz], although we were not able to assign them
specifically to particular stereoisomers. However, four phos-
phorus signals with very similar chemical shifts and dif-
ferent intensity ratio were found in the 31P NMR spectra of
compound 3i, 3m and 3n, whereas three similar phosphorus
signals with different intensity ratio were also observed in
the 31P NMR spectrum of 3k, and all of these signals were
flanked by two sets of satellites for the endocyclic and exo-
cyclic selenium atoms (see Table 2). The results indicate the
presence of some spatial hindrance effects in compounds 3i,
3k, 3m and 3n, compared with compounds 3a–h, 3j and
3l. The hindered rotation of two large Ph(NR1R2)P(Se)CH2
groups from the ortho or meta position in the bridged link-
age benzene backbone in 3i, 3k, 3m and 3n may result in
three or four magnetically different phosphorus environ-
ments rather than three or four chemically different phos-
phorus environments when two potential stereogenic
centres exist. Detailed 31P and 77Se NMR spectroscopic
General: Unless otherwise stated, all reactions were carried out un-
der on oxygen-free nitrogen atmosphere by using predried solvents
and standard Schlenk techniques; subsequent chromatographic and
work up procedures were performed in air. 1H (270 MHz), 13C
(67.9 MHz), 31P{1H} (109 MHz) and 77Se{1H} (51.4 MHz refer-
enced to external Me2Se) NMR spectra were recorded at 25 °C
(unless stated otherwise) with a JEOL GSX 270 instrument. IR
spectra were recorded as KBr pellets in the range of 4000–250 cm–1
with a Perkin–Elmer 2000 FTIR/Raman spectrometer. Mass spec-
trometry was performed by the EPSRC National Mass Spectrome-
try Service Centre, Swansea and the University of St Andrews Mass
Spectrometry Service. X-ray crystal data for 2e and 2j were col-
lected with a Rigaku SCXMIni Mercury CCD system. Intensity
data were collected by using ω steps accumulating area detector
images spanning at least a hemisphere of reciprocal space. All data
were corrected for Lorentz polarization effects. Absorption effects
were corrected on the basis of multiple equivalent reflections or by
semiempirical methods. Structures were solved by direct methods
and refined by full-matrix least-squares against F2 by using the pro-
gram SHELXTL.[36] Hydrogen atoms were assigned riding iso-
tropic displacement parameters and constrained to idealized geo-
metries.
CCDC-944056 (for 2e) and -944057 (for 2i) contain the supplemen-
tary crystallographic data for this paper. These data can be ob-
tained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
General Procedure for the Synthesis of 2a–n: A mixture of amine
(4.0 mmol) and WR (0.54 g, 1.0 mmol) in tetrahydrofuran (60 mL)
was stirred at room temperature for 2 h (the brown suspension dis-
appeared and a pale-yellow suspension formed). To the mixture,
the appropriate haloalkane (2.0 mmol) was added and the mixture
was stirred at room temperature for 24 h. After filtering to remove
insoluble solid and drying in vacuo, the residue was dissolved in
dichloromethane (ca. 2.0 mL) and purified by column chromatog-
raphy on silica gel (dichloromethane/hexane, 1:1) to give the prod-
uct 2a–n.
3
analyses reveal the relatively small coupling constant JP,Se
4
4
= 17.0 Hz and JP,P = 4.2 Hz in 3a, JP,Se = 12.3 Hz in 3b
and 3f, supporting the presence of the P(Se)SeCH2SeP(Se)
or P(Se)SeCH2CH2SeP(Se) linkage in compounds 3a, 3b
and 3f. The 31P and 77Se NMR chemical shifts and coupling
N-Cyclohexyl Se-(2-Oxo-2-phenylethyl) Phenylphosphonamidodi-
selenoate (2a): Yield 0.519 g (54%); yellow oil. IR (KBr): ν = 1670
˜
(vs), 1596 (m), 1579 (m), 1448 (s), 1274 (vs), 1180 (m), 1005 (m),
constants are comparable to those of previously reported 798 (m), 748 (m), 709 (s), 688 (s), 605 (m) cm–1. 1H NMR (CD2Cl2):
phosphorus-selenium compounds.[32–35]
δ = 8.06–7.91 (m, 4 H, Ar-H), 7.61–7.41 (m, 6 H, Ar-H), 4.75 (d,
J{31P-1H} = 13.5 Hz, 2 H, SeCH2), 4.37–4.12 (m, 1 H, cyclohexyl-
H), 3.32–3.20 (m, 1 H, NH), 1.96–0.85 (m, 10 H, cyclohexyl-
H) ppm. 13C NMR (CD2Cl2): δ = 194.9 (C=O), 136.1 (d, JP,C
91.3 Hz), 134.0, 133.1, 132.2 (d, JP,C = 3.1 Hz], 130.9 (d, JP,C
=
=
Conclusions
12.5 Hz), 128.8, 128.7, 128.5 (d, JP,C = 13.5 Hz), 53.0, 37.5, 35.4
(d, JP,C = 19.7 Hz), 35.3 (d, JP,C = 18.7 Hz), 25.1 ppm. 31P NMR
(CD2Cl2): δ = 53.7 (s, JP,Se = 371 Hz, JP,Se = 792 Hz) ppm. 77Se
An efficient route has been developed to prepare a series
of new Se-alkylphenylphosphonamido-diselenoate and alk-
ane bis(N-alkyl-P-phenylphosphonamido-diselenoate) de-
rivatives in moderate to good yields from the reaction of
NMR (CD2Cl2): δ = 345.4 (d, JP,Se = 371 Hz), –102.0 (d, JP,Se
=
792 Hz) ppm. MS (CI+): m/z = 486 [M + H]+. HRMS (CI+): calcd
ammonium phenylphosphonamido-diselenoates or phenyl- for C20H24NOPSe2H [M + H]+ 486.0002; found 485.9994.
4
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Organophosphorus-Selenium Heteroatom Derivatives
N-Cyclohexyl Se-Undecyl Phenylphosphonamidodiselenoate (2b):
(C=O), 137.7 (d, JP,C = 91.3 Hz), 134.4, 132.1, 131.2, 131.0, 130.4,
Yield 0.433 g (42%); pale-yellow oil. IR (KBr): ν = 1446 (m), 1436 128.6, 128.4, 58.0, 38.5, 31.1 ppm. 31P NMR (CD2Cl2): δ = 46.9 (s,
˜
(m), 1403 (m), 1292 (m), 1231 (m), 1136 (m), 1081 (s), 994 (m), 877 JP,Se = 355 Hz, JP,Se = 794 Hz) ppm. 77Se NMR (CD2Cl2): δ = 384.0
1
(m), 745 (s), 690 (s), 560 (s), 524 (s) cm–1. H NMR (CD2Cl2): δ =
(d, JP,Se = 355 Hz), –53.0 (d, JP,Se = 792 Hz) ppm. MS (ES+): m/z
8.05–7.97 (m, 2 H, Ar-H), 7.49–7.45 (m, 3 H, Ar-H), 3.40 (dt, JH,H = 560 [M + Na]+. HRMS (ES+): calcd for C18H21BrNONaPSe2
= 7.4 Hz, 1 H, cyclohexyl-H), 3.22–3.12 (m, 2 H, cyclohexyl-H), [M + Na]+ 559.8772; found 559.8767.
2.92–2.84 (m, JP,H = 13.2 Hz, JH,H = 7.4 Hz, 2 H, SeCH2), 2.71 (t,
N-sec-Butyl Se-[2-(4-Bromophenyl)-2-oxoethyl] Phenylphosphon-
JH,H = 7.4 Hz, 2 H, CH2), 1.96 (d, JH,H = 9.4 Hz, 1 H, NH), 1.71–
amidodiselenoate (2f): Yield 0.500 g (93%); reddish yellow sticky
1.19 (m, 24 H, cyclohexyl-H, CH2), 0.87 (t, JH,H = 6.6 Hz, 3 H,
oil. Two stereoisomers were found in ca. 1:1 intensity ratio. IR
CH3) ppm. 13C NMR (CD2Cl2: δ = 137.3 (d, JP,C = 87.2 Hz), 131.9
(KBr): ν = 1671 (s), 1583 (s), 1435 (m), 1397 (s), 1273 (s), 1178 (s),
˜
1098 (m), 1070 (s), 1004 (s), 838 (m), 746 (s), 689 (m), 538 (s) cm–1.
1H NMR (CD2Cl2): δ = 8.04–7.94 (m, 2ϫ2 H, Ar-H), 7.81–7.75
(m, 2ϫ2 H, Ar-H), 7.61–7.54 (m, 2ϫ2 H, Ar-H), 7.49–7.45 (m, 3
H, Ar-H), 4.27–3.91 (m, 2ϫ1 H, CH), 3.51–3.05 (m, 2ϫ2 H,
SeCH2), 2.54 (d, JH,H = 9.5 Hz, 2ϫ1 H, NH), 1.59–1.41 (m, 2ϫ2
H, CH2), 1.13 (dd, JH,H = 6.6 Hz, JP,H = 3.3 Hz, 3 H, CH3), 1.12
(dd, JH,H = 6.6 Hz, JP,H = 3.3 Hz, 3 H, CH3), 0.88 (t, JH,H = 7.4 Hz,
3 H, CH3), 0.85 (t, JH,H = 7.4 Hz, 3 H, CH3) ppm. 13C NMR
(CD2Cl2): δ = 194.4 (C=O), 136.3 (d, JP,C = 89.4 Hz), 136.2 (d, JP,C
(d, JP,C = 3.1 Hz), 130.8 (d, JP,C = 12.5 Hz), 128.4 (d, JP,C
=
13.5 Hz), 52.8, 35.7 (d, JP,C = 5.2 Hz), 35.6 (d, JP,C = 5.2 Hz), 32.9,
32.0, 30.5 (d, JP,C = 3.1 Hz), 29.9, 29.6, 29.5, 29.4, 29.1, 25.5, 25.2,
22.8, 14.0 ppm. 31P NMR (CD2Cl2): δ = 53.2 (s, JP,Se = 391 Hz,
JP,Se = 786 Hz) ppm. 77Se NMR (CD2Cl2): δ = 323.6 (d, JP,Se
=
391 Hz), –104.5 (d, JP,Se = 786 Hz) ppm. MS (CI+): m/z = 522 [M
+ H]+. HRMS (CI+): calcd for C23H40NPSe2H [M + H]+ 522.1303;
found 522.1299.
N-Cyclohexyl Se-Nonyl Phenylphosphonamidodiselenoate (2c):
= 90.6 Hz), 134.6, 134.5, 132.6 (d, JP,C = 3.1 Hz), 132.5 (d, JP,C
=
Yield 0.405 g (41%); colourless oil. IR (KBr): ν = 1447 (m), 1436
˜
3.1 Hz), 132.4, 132.3, 132.2, 131.5, 131.4, 131.3, 131.2, 130.7, 130.6,
(m), 1404 (m), 1293 (m), 1231 (m), 1142 (m), 1081 (s), 994 (m), 878
129.1, 129.0, 128.3, 128.7, 51.7 (d, JP,C = 18.9 Hz), 51.4 (d, JP,C
18.7 Hz), 38.1, 37.5, 31.8 (d, JP,C = 23.6 Hz), 31.7 (d, JP,C
=
=
1
(m), 746 (s), 690 (s), 569 (s), 524 (s) cm–1. H NMR (CD2Cl2): δ =
8.05–7.97 (m, 2 H, Ar-H), 7.49–7.45 (m, 3 H, Ar-H), 3.40 (dt, JH,H
= 7.4 Hz, 1 H, cyclohexyl-H), 3.22–3.12 (m, 2 H, cyclohexyl-H),
2.92–2.84 (m, JP,H = 13.2 Hz, JH,H = 7.4 Hz, 2 H, SeCH2), 2.72 (t,
JH,H = 7.4 Hz, 2 H, CH2), 1.96 (d, JH,H = 9.4 Hz, 1 H, NH), 1.71–
1.18 (m, 20 H, cyclohexyl-H, CH2), 0.87 (t, JH,H = 6.6 Hz, 3 H,
CH3) ppm. 13C NMR (CD2Cl2): δ = 137.3 (d, JP,C = 86.2 Hz), 131.8
22.1 Hz), 22.2 (d, JP,C = 21.4 Hz), 22.1 (d, JP,C = 20.5 Hz), 10.5,
10.4 ppm. 31P NMR (CD2Cl2): δ = 56.0 (s, JP,Se = 366 Hz, JP,Se
=
796 Hz), 54.8 (s, JP,Se = 373 Hz, JP,Se = 782 Hz) ppm. 77Se NMR
(CD2Cl2): δ = 348.5 (d, JP,Se = 374 Hz), 346.1 (d, JP,Se = 367 Hz),
–101.9 (d, JP,Se = 794 Hz), –104.8 (d, JP,Se = 784 Hz) ppm. MS
(ES+): m/z
= 560 [M +
Na]+. HRMS (ES+): calcd for
(d, JP,C = 3.1 Hz), 130.8 (d, JP,C = 12.5 Hz), 128.3 (d, JP,C
=
C18H21BrNONaPSe2 [M + Na]+ 559.8772; found 559.8762.
13.5 Hz), 52.8, 35.6 (d, JP,C = 5.2 Hz), 35.5 (d, JP,C = 5.2 Hz), 32.9,
31.9, 30.5 (d, JP,C = 3.1 Hz), 29.9, 29.5, 29.4, 29.3, 25.5, 25.2, 22.8,
N-Butyl Se-[2-(4-Bromophenyl)-2-oxoethyl] Phenylphosphonamido-
diselenoate (2g): Yield 0.434 g (81%); yellow sticky oil. IR (KBr):
14.0 ppm. 31P NMR (CD2Cl2): δ = 53.2 (s, JP,Se = 390 Hz, JP,Se
=
786 Hz) ppm. 77Se NMR (CD2Cl2): δ = 323.6 (d, JP,Se = 390 Hz),
–104.6 (d, JP,Se = 786 Hz) ppm. MS (CI+): m/z = 494 [M + H]+.
HRMS (CI+): calcd for C21H36NPSe2H [M + H]+ 494.0990; found
494.0892.
ν = 1657 (s), 1585 (s), 1435 (m), 1396 (m), 1279 (s), 1100 (m), 1085
˜
(m), 1069 (m), 1004 (s), 841 (m), 752 (s), 705 (m), 689 (m), 567 (s),
1
441 (m) cm–1. H NMR (CD2Cl2): δ = 8.00–7.92 (m, 2 H, Ar-H),
7.81 (d, JH,H = 6.9 Hz, 2 H, Ar-H), 7.61 (d, JH,H = 6.9 Hz, 2 H,
Ar-H), 7.50–7.47 (m, 3 H, Ar-H), 4.31–4.15 (m, 2 H, NHCH2),
3.18 (br. s, 1 H, NH), 2.91 (d, 2 H, SeCH2), 1.62–1.28 (m, 4 H,
cyclohexyl-H), 0.87 (t, JH,H = 7.4 Hz, 3 H, CH3) ppm. 13C NMR
(CD2Cl2): δ = 194.4 (C=O), 135.4 (d, JP,C = 89.9 Hz), 134.5, 132.8
(d, JP,C = 3.1 Hz), 132.4, 131.1 (d, JP,C = 12.5 Hz), 130.7, 129.1 (d,
JP,C = 13.5 Hz), 43.5 (d, JP,C = 3.7 Hz), 37.2, 33.3 (d, JP,C = 9.5 Hz),
20.4, 13.9 ppm. 31P NMR (CD2Cl2): δ = 58.0 (s, JP,Se = 370 Hz,
N-Cyclohexyl Se-Heptyl Phenylphosphonamidodiselenoate (2d):
Yield 0.272 g (59%); colourless oil. IR (KBr): ν = 1450 (m), 1436
˜
(m), 1404 (m), 1293 (m), 1231 (m), 1140 (m), 1081 (vs), 994 (m),
1
878 (m), 746 (s), 690 (s), 570 (s), 523 (s) cm–1. H NMR (CD2Cl2):
δ = 8.06–7.97 (m, 2 H, Ar-H), 7.50–7.45 (m, 3 H, Ar-H), 3.17–3.12
(m, 1 H, cyclohexyl-H), 2.89 (dt, JP,H = 13.2 Hz, JH,H = 7.4 Hz, 2
H, SeCH2), 2.72 (t, JH,H = 7.4 Hz, 2 H, CH2), 1.96 (d, JH,H
=
JP,Se = 794 Hz) ppm. 77Se NMR (CD2Cl2): δ = 321.2 (d, JP,Se
=
9.4 Hz, 1 H, NH), 1.69–1.09 (m, 18 H, cyclohexyl-H, CH2), 0.86
370 Hz), –100.4 (d, JP,Se = 794 Hz) ppm. MS (ES+): m/z = 560 [M
+ Na]+. HRMS (ES+): calcd for C18H21NONaBrPSe2 [M + Na]+
559.8772; found 559.8771.
(t, JH,H = 6.6 Hz, 3 H, CH3) ppm. 13C NMR (CD2Cl2): δ = 137.2
(d, JP,C = 87.2 Hz], 131.9 (d, JP,C = 3.1 Hz), 130.8 (d, JP,C
=
12.5 Hz), 128.4 (d, JP,C = 13.5 Hz), 52.9, 35.7 (d, JP,C = 5.2 Hz),
35.6 (d, JP,C = 5.2 Hz), 32.9, 31.7, 30.5 (d, JP,C = 3.1 Hz), 29.9,
N-Cyclohexyl Se-[2-(4-Bromophenyl)-2-oxoethyl] Phenylphosphon-
amidodiselenoate (2h): Yield 0.630 g (56%); brown paste. IR (KBr):
28.8, 25.3, 22.7, 13.9 ppm. 31P NMR (CD2Cl2): δ = 53.2 (s, JP,Se
=
ν = 1673 (s), 1584 (s), 1483 (m), 1435 (m), 1396 (m), 1270 (s), 1178
˜
390 Hz, JP,Se = 786 Hz) ppm. 77Se NMR (CD2Cl2): δ = 323.6 (d,
JP,Se = 391 Hz), –104.4 (d, JP,Se = 786 Hz) ppm. MS (ES+): m/z =
488 [M + Na]+. HRMS (ES+): calcd for C19H32NNaPSe2 [M +
Na]+ 488.0500; found 488.0500.
1
(m), 1071 (s), 1004 (s), 836 (m), 747 (s), 689 (m), 519 (s) cm–1. H
NMR (CD2Cl2): δ = 8.02–7.97 (m, 2 H, Ar-H), 7.80–7.78 (m, 2 H,
Ar-H), 7.62–7.58 (m, 2 H, Ar-H), 7.50–7.43 (m, 3 H, Ar-H), 4.30–
4.14 (m, 1 H, cyclohexyl-H), 3.23 (br. s, 1 H, NH), 2.59–2.52 (d,
2 H, SeCH2), 2.05–0.86 (m, 10 H, cyclohexyl-H) ppm. 13C NMR
(CD2Cl2): δ = 194.3 (C=O), 136.3 (d, JP,C = 90.0 Hz), 134.5, 132.6
N-tert-Butyl Se-[2-(4-Bromophenyl)-2-oxoethyl] Phenylphosphon-
amidodiselenoate (2e): Yield 0.440 g (82%); pale-yellow paste. IR
(KBr): ν = 1669 (s), 1582 (s), 1564 (m), 1474 (m), 1437 (m), 1385 (d, JP,C = 3.1 Hz), 132.4, 131.1 (d, JP,C = 12.5 Hz), 130.7, 129.1 (d,
˜
(m), 1363 (m), 1270 (m), 1222 (m), 1188 (s), 1095 (m), 1070 (m), JP,C = 13.5 Hz), 53.1 (d, JP,C = 18.1 Hz), 37.8, 35.8, 29.0, 25.3 ppm.
1
983 (s), 804 (m), 747 (s), 691 (s), 546 (m), 528 (s) cm–1. H NMR 31P NMR (CD2Cl2):
δ
=
54.5 (s, JP,Se
= 369 Hz, JP,Se =
(CD2Cl2): δ = 8.12–8.04 (m, 2 H, Ar-H), 7.84 (d, JH,H = 8.8 Hz, 2
794 Hz) ppm. 77Se NMR (CD2Cl2): δ = 347.7 (d, JP,Se = 369 Hz),
H, Ar-H), 7.60 (d, JH,H = 8.8 Hz, 2 H, Ar-H), 7.51–7.43 (m, 3 H, –100.7 (d, JP,Se = 794 Hz) ppm. MS (CI+): m/z = 564 [M + H]+.
Ar-H), 4.37 (d, JP,H = 13.2 Hz, 2 H, SeCH2), 2.54 (d, JH,H = 9.5 Hz,
HRMS (CI+): calcd for C20H23BrNOPSe2H [M + H]+ 563.9109;
found 563.9111.
1 H, NH), 1.30 (s, 9 H, CH3) ppm. 13C NMR (CD2Cl2): δ = 194.3
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
5

Job/Unit: O30860
/KAP1
Date: 23-09-13 17:45:29
Pages: 10
G. Hua, K. S. A. Arachchige, A. M. Z. Slawin, J. D. Woollins
FULL PAPER
N-Cyclopentyl Se-[2-(4-Bromophenyl)-2-oxoethyl] Phenylphosphon-
amidodiselenoate (2i): Yield 0.445 g (81%); greyish yellow paste. IR
6 H, CH3) ppm. 13C NMR (CD2Cl2): δ = 193.9 (C=O), 135.2 (d,
JP,C = 112.1 Hz), 132.3, 132.1, 132.0 (d, JP,C = 3.1 Hz), 131.9, 130.2
(d, JP,C = 12.5 Hz), 129.5, 128.3 (d, JP,C = 13.5 Hz), 55.3, 38.9, 26.8,
(KBr): ν = 1658 (s)m, 1581 (s), 1434 (m), 1416 (m), 1395 (m), 1278
˜
(s), 1177 (m), 1093 (m), 1068 (m), 1004 (s), 840 (s), 752 (s), 704 20.3 ppm. 31P NMR (CD2Cl2): δ = 78.4 (s, JP,Se = 362 Hz, JP,Se
=
(m), 687 (m), 621 (m), 555 (s), 463 (s), 418 (m) cm–1. 1H NMR 798 Hz) ppm. 77Se NMR (CD2Cl2): δ = 299.8 (d, JP,Se = 362 Hz),
(CD2Cl2): δ = 8.02–7.93 (m, 2 H, Ar-H), 7.81 (d, JH,H = 6.9 Hz, 2
–93.5 (d, JP,Se = 799 Hz) ppm. MS (ES+): m/z = 616 [M + Na]+.
H, Ar-H), 7.58 (d, JH,H = 6.9 Hz, 2 H, Ar-H), 7.52–7.42 (m, 3 H, HRMS (ES+): calcd for C22H29NONaBrPSe2 [M + Na]+ 615.9398;
Ar-H), 4.32–4.12 (m, 1 H, cyclopentyl-H), 3.31 (dd, 1 H, NH), 2.54 found 615.9409.
(d, 2 H, SeCH2), 1.94–1.45 (m, 8 H, cyclopentyl-H) ppm. 13C NMR
N,N-Diisopropyl Se-[2-(Hydroxymethyl)benzyl] Phenylphosphon-
amidodiselenoate (2m): Yield 0.215 g (44%); yellow paste. IR (KBr):
(CD2Cl2): δ = 194.1 (d, JP,C = 3.4 Hz, C=O), 135.6 (d, JP,C
90.3 Hz), 134.2, 132.4 (d, JP,C = 3.1 Hz), 132.0, 130.9 (d, JP,C
=
=
ν = 1486 (m), 1453 (m), 1435 (m), 1172 (m), 1040 (m), 759 (s), 711
˜
12.5 Hz), 130.4, 128.7 (d, JP,C = 13.5 Hz), 55.8 (d, JP,C = 4.2 Hz),
37.2, 34.8 (d, JP,C = 6.2 Hz), 23.3 (d, JP,C = 7.3 Hz) ppm. 31P NMR
(CD2Cl2): δ = 55.8 (s, JP,Se = 369 Hz, JP,Se = 791 Hz) ppm. 77Se
1
(m), 550 (s), 507 (m), 442 (m) cm–1. H NMR (CD2Cl2): δ = 8.01–
7.94 (m, 2 H, Ar-H), 7.35–7.22 (m, 7 H, Ar-H), 4.67 (d, JH,H
=
15.4 Hz, 2 H, CH2), 3.96–3.85 (m, 2 H, CH), 3.70 (t, 1 H, OH), 2.59
(d, 2 H, SeCH2), 1.29 (dd, 12 H, CH3) ppm. 13C NMR (CD2Cl2): δ
= 139.2, 136.7, 133.5, 131.5, 131.2, 131.0, 130.3, 128.8, 127.7, 127.3,
NMR (CD2Cl2): δ = 338.8 (d, JP,Se = 369 Hz), –95.3 (d, JP,Se
=
791 Hz) ppm. MS (ES+): m/z = 572 [M + Na]+. HRMS (ES+):
calcd for C19H21NONaBrPSe2 [M
571.8766.
+
Na]+ 571.8772; found
62.6, 50.0, 29.9, 22.8 ppm. 31P NMR (CD2Cl2); δ = 59.9 (s, JP,Se
=
387 Hz, JP,Se = 777 Hz) ppm. 77Se NMR (CD2Cl2): δ = 361.4 (d,
JP,Se = 388 Hz), –26.4 (d, JP,Se = 777 Hz) ppm. MS (CI+): m/z =
490 [M + H]+. HRMS (CI+): calcd for C20H28NOPSe2H [M +
H]+ 490.0315; found 490.0308.
N-Isopropyl Se-[2-(4-Bromophenyl)-2-oxoethyl] Phenylphosphon-
amidodiselenoate (2j): Yield 0.460 g (88%); light-yellow paste. IR
(KBr): ν = 1656 (s), 1580 (s), 1563 (m), 1413 (s), 1277 (s), 1124
˜
(m), 1094 (m), 1068 (m), 1029 (m), 1004 (s), 748 (s), 703 (m), 687
(m), 622 (m), 565 (s), 473 (m), 585 (m), 420 (m) cm–1. 1H NMR
(CD2Cl2): δ = 8.01 (dd, JP,H = 14.9 Hz, JH,H = 8.0 Hz, 2 H, Ar-H),
7.80 (d, JH,H = 8.5 Hz, 2 H, Ar-H), 7.60 (d, JH,H = 8.5 Hz, 2 H,
Ar-H), 7.52–7.43 (m, 3 H, Ar-H), 4.31–4.08 (m, 1 H, CH), 3.65–
3.52 (m, 2 H, SeCH2), 3.19 (br., 1 H, NH), 1.15 (d, JH,H = 6.1 Hz,
6 H, CH3) ppm. 13C NMR (CD2Cl2): δ = 194.0 (C=O), 135.8 (d,
JP,C = 90.3 Hz, Ar-C), 134.2 (Ar-C), 132.3 (d, JP,C = 3.1 Hz, Ar-
C), 132.1 (Ar-C), 130.9 (d, JP,C = 12.5 Hz, Ar-C), 130.4 (Ar-C),
128.6 (d, JP,C = 13.5 Hz, Ar-C), 46.2 (N-C), 37.4 (Se-C), 25.0 (d,
JP,C = 5.2 Hz, CH3), 24.6 (d, JP,C = 5.2 Hz, CH3) ppm. 31P NMR
(CD2Cl2): δ = 54.6 (s, JP,Se = 369 Hz, JP,Se = 794 Hz) ppm. 77Se
N-Benzyl Se-[2-(4-Bromophenyl)-2-oxoethyl] Phenylphosphonamido-
diselenoate (2n): Yield 0.534 g (47%); yellow paste. IR (KBr): ν =
˜
1693 (vs), 1580 (s), 1479 (m), 1453 (m), 1434 (m), 1394 (m), 1274
(m), 1189 (m), 1100 (m), 1056 (s), 984 (s), 801 (s), 731 (s), 686 (s),
1
555 (s), 492 (m), 475 (m), 445 (m) cm–1. H NMR (CD2Cl2): δ =
8.03 (d, JH,H = 8.26 Hz, 2 H, Ar-H), 7.81–7.77 (m, 2 H, Ar-H),
7.60–7.47 (m, 5 H, Ar-H), 7.36–7.26 (m, 5 H, Ar-H), 4.31–4.01 (m,
4 H, CH2), 3.68–3.60 (m, 1 H, NH) ppm. 13C NMR (CD2Cl2): δ =
193.9 (C=O), 138.7, 138.5, 134.8 (d, JP,C = 91.3 Hz), 132.6 (d, JP,C
= 3.1 Hz), 132.1, 130.9 (d, JP,C = 12.5 Hz), 130.4 (d, JP,C
=
13.5 Hz), 129.9, 128.9, 128.7, 128.1, 127.6, 46.9, 37.2 ppm. 31P
NMR (CD2Cl2): δ = 58.3 (s, JP,Se = 376 Hz, JP,Se = 798 Hz) ppm.
77Se NMR (CD2Cl2): δ = 324.8 (d, JP,Se = 376 Hz), –103.4 (d, JP,Se
= 798 Hz) ppm. MS (ES+): m/z = 594 [M + Na]+. HRMS (CI+):
calcd for C21H19NOPSe2BrH [M + H]+ 571.8790; found 571.8787.
NMR (CD2Cl2): δ = 345.3 (d, JP,Se = 370 Hz), –102.4 (d, JP,Se
=
794 Hz) ppm. MS (CI+): m/z = 524 [M + H]+. HRMS (CI+): calcd
for C17H19BrNOPSe2H [M + H]+ 523.8789; found 523.8791.
N,N-Diisopropyl Se-[2-(4-Bromophenyl)-2-oxoethyl] Phenylphos-
phonamidodiselenoate (2k): Yield 0.310 g (55%); yellow paste. IR
General Procedure for the Synthesis of 3a–n: A mixture of amine
(4.0 mmol) and WR (0.54 g, 1.0 mmol) in THF (60 mL) was stirred
at room temperature for 2 h (the brown suspension disappeared
and a pale-yellow suspension formed). To the mixture, the appro-
priate dihaloalkane (1.0 mmol) was added and the mixture was
stirred at room temperature for 24 h. After filtering to remove in-
soluble solid and drying in vacuo, the residue was dissolved in
dichloromethane (ca. 2.0 mL) and purified by column chromatog-
raphy on silica gel (dichloromethane) to give the product 3a–n.
(KBr): ν = 1682 (s), 1585 (s), 1434 (m), 1394 (s), 1362 (m), 1266
˜
(s), 1174 (m), 1105 (m), 1071 (s), 1007 (s), 821 (s), 747 (s), 588 (m),
559 (m), 496 (m), 454 (m) cm–1. 1H NMR (CD2Cl2): δ = 7.82–7.80
(m, 2 H, Ar-H), 7.78 (d, JH,H = 6.9 Hz, 2 H, Ar-H), 7.61 (d, JH,H
= 6.9 Hz, 2 H, Ar-H), 7.58–7.54 (m, 3 H, Ar-H), 4.39–4.34 (m, 2
H, CH), 2.54 (d, 2 H, SeCH2), 1.46 (d, JH,H = 6.4 Hz, 12 H,
CH3) ppm. 13C NMR (CD2Cl2): δ = 194.1 (C=O), 133.5 (d, JP,C
112.1 Hz), 132.1, 131.9, 131.6 (d, JP,C = 3.1 Hz), 131.2 (d, JP,C
=
=
Methylene
Bis(N-cyclohexyl-P-phenylphosphonamidodiselenoate)
12.5 Hz), 130.5, 130.2, 128.3 (d, JP,C = 13.5 Hz), 50.0, 39.3,
(3a): Yield 0.585 g (79%); pale-yellow oil. A pair of diastereoiso-
mers was found in multinuclear NMR spectra in ca. 1:1 intensity
22.8 ppm. 31P NMR (CD2Cl2): δ = 62.5 (s, JP,Se = 366 Hz, JP,Se
=
789 Hz) ppm. 77Se NMR (CD2Cl2): δ = 311.7 (d, JP,Se = 367 Hz),
–26.1 (d, JP,Se = 789 Hz) ppm. MS (CI+): m/z = 566 [M + H]+.
HRMS (CI+): calcd for C20H24BrNOPSe2H [M + H]+ 565.9266;
found 565.9269.
ratio. IR (KBr): ν = 1435 (s), 1403 (m), 1292 (m), 1231 (m), 1139
˜
(m), 1077 (vs), 994 (s), 902 (s), 879 (s), 745 (s), 688 (s), 567 (s), 518
1
(vs), 490 (s), 438 (m) cm–1. H NMR (CD2Cl2): δ = 8.01–7.88 (m,
2ϫ4 H, Ar-H), 7.60–7.39 (m, 2ϫ6 H, Ar-H), 4.42–4.20 (m, 2ϫ2
H, cyclohexyl-H), 3.21 (d, 2 H, SeCH2), 3.05 (d, 2 H, SeCH2), 1.96–
0.83 (m, 2ϫ20 H, NH, cyclohexyl-H) ppm. 13C NMR (CD2Cl2): δ
N,N-Diisobuyl Se-[2-(4-Bromophenyl)-2-oxoethyl] Phenylphos-
phonamidodiselenoate (2l): Yield 0.398 g (67%); reddish yellow
sticky oil. IR (KBr): ν = 1683 (s), 1585 (s), 1465 (m), 1434 (m), = 136.2 (d, JP,C = 88.2 Hz), 132.3 (d, JP,C = 3.1 Hz), 130.9 (d, JP,C
˜
1394 (m), 1267 (s), 1177 (m), 1156 (m), 1094 (s), 1070 (s), 1009 (s), = 12.5 Hz), 128.6 (d, JP,C = 13.5 Hz), 53.1 (d, JP,C = 9.5 Hz), 35.6,
876 (m), 819 (m), 745 (s), 704 (m), 690 (m), 575 (s), 490 (m) cm–1. 29.1, 25.4, 25.2 ppm. 31P NMR (CD2Cl2): δ = 54.9 (s, JP,Se
=
=
1H NMR (CD2Cl2): δ = 8.02 (dd, JP,H = 14.6 Hz, JH,H = 6.6 Hz, 2
374 Hz, JP,Se = 791 Hz), 54.8 (s, JP,Se = 371 Hz, JP,Se
H, Ar-H), 7.81 (d, JH,H = 6.9 Hz, 2 H, Ar-H), 7.59 (d, JH,H
6.9 Hz, 2 H, Ar-H), 7.51–7.42 (m, 3 H, Ar-H), 4.27 (d, JP,H
10.8 Hz, 2 H, SeCH2), 2.94–2.81 (m, 4 H, NCH2), 1.89–1.81 (m, 2
=
=
791 Hz) ppm. 77Se NMR (CD2Cl2): δ = 398.6 (d, JP,Se = 371 Hz),
395.5 (d, JP,Se = 374 Hz), –91.9 (d, JP,Se = 791 Hz), –92.7 (d, JP,Se
= 791 Hz) ppm. MS (CI+): m/z = 745 [M + H]+. HRMS (CI+):
calcd for C25H37N2P2Se4 [M + H] 744.9101; found 744.9099.
H, CH), 0.81 (d, JH,H = 6.6 Hz, 6 H, CH3), 0.75 (d, JH,H = 6.6 Hz,
6
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Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O30860
/KAP1
Date: 23-09-13 17:45:29
Pages: 10
Organophosphorus-Selenium Heteroatom Derivatives
Ethane-1,2-diyl Bis(N-cyclohexyl-P-phenylphosphonamidodiseleno-
ate) (3b): Yield 0.604 g (80%); pale-yellow oil. A pair of diastereo-
isomers was found in multinuclear NMR spectra in ca. 1:1 intensity
25.2 ppm. 31P NMR (CD2Cl2): δ = 53.9 (s, JP,Se = 386 Hz, JP,Se
=
789 Hz), 53.8 (s, JP,Se = 386 Hz, JP,Se = 789 Hz) ppm. 77Se NMR
(CD2Cl2): δ = 395.9 (d, JP,Se = 386 Hz), 395.1 (d, JP,Se = 386 Hz),
–96.7 (d, JP,Se = 789 Hz), –96.8 (d, JP,Se = 789 Hz) ppm. MS (CI+):
ratio. IR (KBr): ν = 1434 (m), 1405 (m), 1077 (s), 994 (m), 878 (m),
˜
745 (m), 688 (s), 519 (s), 479 (m), 443 (m) cm–1. 1H NMR (CD2Cl2): m/z = 835 [M + H]+. HRMS (C|I+): calcd for C32H43N2PSe4 [M +
δ = 8.12–7.90 (m, 2ϫ4 H, Ar-H), 7.50–7.43 (m, 2ϫ6 H, Ar-H), H] 834.9580; found 834.9569.
4.36–4.06 (dd, 2ϫ2 H, cyclohexyl-H), 3.20–3.08 (m, 2ϫ4 H,
Ethane-1,2-diyl Bis(N-isopropyl-P-phenylphosphonamidodiseleno-
CH2Se), 2.28–1.17 (m, 2ϫ22 H, NH, cyclohexyl-H) ppm. 13C
ate) (3f): Yield 0.440 g (55%); reddish pink paste. A pair of dia-
NMR (CD2Cl2): δ = 135.7 (d, JP,C = 90.3 Hz), 135.6 (d, JP,C
=
stereoisomers was found in multinuclear NMR spectra in ca. 2:3
90.3 Hz), 132.2 (d, JP,C = 3.1 Hz), 132.5 (d, JP,C = 3.1 Hz), 130.9
(d, JP,C = 12.5 Hz), 130.8 (d, JP,C = 12.5 Hz), 128.6, 130.9 (d, JP,C
= 13.5 Hz), 53.0, 52.9, 35.7, 35.6, 32.1, 30.9, 25.4, 25.3 ppm. 31P
NMR (CD2Cl2): δ = 52.5 (s, JP,Se = 384 Hz, JP,Se = 784 Hz), 52.4
(s, JP,Se = 386 Hz, JP,Se = 786 Hz) ppm. 77Se NMR (CD2Cl2): δ =
378.5 (d, JP,Se = 384 Hz), 375.6 (d, JP,Se = 386 Hz), –90.1 (d, JP,Se
= 784 Hz), –94.7 (d, JP,Se = 786 Hz) ppm. MS (CI+): m/z = 759 [M
+ H]+. HRMS (CI+): calcd for C26H39N2P2Se4 [M + H] 758.9256;
found 758.9260.
intensity ratio. IR (KBr): ν = 1436 (s), 1398 (m), 1160 (m), 1130
˜
(s), 1027 (s), 946 (m), 890 (m), 747 (s), 692 (s), 586 (s), 537 (s) cm–1.
1H NMR (CD2Cl2): δ = 7.88–7.79 (m, 2ϫ4 H, Ar-H), 7.50–7.43
(m, 2ϫ6 H, Ar-H), 4.25–4.05 (m, 2ϫ2 H, CH), 3.60–3.57 (m, 2ϫ4
H, SeCH2), 3.19–3.16 (m, 2ϫ2 H, NH), 1.38–1.34 (m, 2ϫ12 H,
CH3) ppm. 13C NMR (CD2Cl2): δ = 137.1, 136.5, 131.6 (d, JP,C
= 3.1 Hz), 130.8, 130.6, 128.3, 128.1, 61.9, 61.8, 45.3, 44.7, 25.2,
24.7 ppm. 31P NMR (CD2Cl2): δ = 53.0 (s, JP,Se = 383 Hz, JP,Se
=
786 Hz), 52.7 (s, JP,Se = 385 Hz, JP,Se = 784 Hz) ppm. 77Se NMR
(CD2Cl2): δ = 514.7 (d, JP,Se = 385 Hz), 514.5 (d, JP,Se = 383 Hz),
–248.5 (d, JP,Se = 784 Hz), –248.7 (d, JP,Se = 786 Hz) ppm. MS
(CI+): m/z = 679 [M + H]+. HRMS (C|I+): calcd for C20H31N2PSe4
[M + H] 678.8631; found 678.8625.
Propane-1,3-diyl Bis(N-cyclohexyl-P-phenylphosphonamidodiseleno-
ate) (3c): Yield 0.540 g (70%); pale-yellow paste. A pair of dia-
stereoisomers was found in multinuclear NMR spectra in ca. 1:1
intensity ratio. IR (KBr): ν = 1435 (m), 1403 (m), 1289 (m), 1229
˜
(m), 1078 (vs), 994 (m), 878 (m), 745 (s), 689 (s), 568 (m), 520 (s),
Propane-1,3-diyl Bis(N-isopropyl-P-phenylphosphonamidodiseleno-
ate) (3g): Yield 0.380 g (55%); reddish yellow paste. A pair of dia-
stereoisomers was found in multinuclear NMR spectra in ca. 1:1
1
489 (m) cm–1. H NMR (CD2Cl2): δ = 8.03–7.95 (m, 2ϫ4 H, Ar-
H), 7.53–7.451 (m, 2ϫ6 H, Ar-H), 3.28–3.11 (m, 2ϫ2 H, cyclo-
hexyl-H), 2.96–2.76 (m, 2ϫ6 H, SeCH2, NH), 2.14–1.07 (m, 2ϫ22
intensity ratio. IR (KBr): ν = 163 (w), 1435 (m), 1285 (m), 1114
˜
H, cyclohexyl-H) ppm. 13C NMR (CD2Cl2): δ = 137.1 (d, JP,C
=
(m), 1029 (s), 893 (s), 806 (s), 747 (m), 691 (s), 542 (m) cm–1. 1H
NMR (CD2Cl2): δ = 8.03–7.94 (m, 2ϫ4 H, Ar-H), 7.54–7.47 (m,
2ϫ6 H, Ar-H), 3.90–3.52 (m, 2ϫ2 H, CH), 3.30–3.24 (m, 2ϫ4
H, SeCH2), 2.98–2.88 (m, 2ϫ2 H, NH), 1.52–1.37 (m, 2ϫ2 H,
CH2), 1.17–1.12 (m, 2ϫ12 H, CH3) ppm. 13C NMR (CD2Cl2): δ
= 136.8, 136.2, 135.5, 135.1, 132.6 (d, JP,C = 3.1 Hz), 132.1 (d, JP,C
= 3.1 Hz), 131.1, 130.9, 130.7, 130.5, 129.1, 128.9, 18.6, 128.4, 46.2,
45.8, 29.1, 29.0, 25.0, 24.5, 20.9 ppm. 31P NMR (CD2Cl2): δ = 53.9
88.2 Hz), 132.0 (d, JP,C = 3.1 Hz), 130.8 (d, JP,C = 12.5 Hz), 128.5
(d, JP,C = 13.5 Hz), 53.0, 35.6, 32.3, 31.2, 25.4, 25.3 ppm. 31P NMR
(CD2Cl2): δ = 53.7 (s, JP,Se = 384 Hz, JP,Se = 789 Hz), 53.6 (s, JP,Se
= 386 Hz, JP,Se = 786 Hz) ppm. 77Se NMR (CD2Cl2): δ = 325.1 (d,
JP,Se = 384 Hz), 324.8 (d, JP,Se = 386 Hz), –102.8 (d, JP,Se = 789 Hz),
–103.5 (d, JP,Se = 786 Hz) ppm. MS (CI+): m/z = 773 [M + H]+.
HRMS (CI+): calcd for C27H41N2P2Se4 [M + H] 772.9421; found
772.9416.
(s, JP,Se = 385 Hz, JP,Se = 789 Hz), 53.8 (s, JP,Se = 385 Hz, JP,Se
=
789 Hz) ppm. 77Se NMR (CD2Cl2): δ = 323.4 (d, JP,Se = 385 Hz),
323.0 (d, JP,Se = 385 Hz), –164.2 (d, JP,Se = 789 Hz), –173.8 (d, JP,Se
= 786 Hz) ppm. MS (CI+): m/z = 693 [M + H]+. HRMS (C|I+):
calcd for C21H33N2PSe4 [M + H] 692.8788; found 692.8779.
Butane-1,4-diyl Bis(N-cyclohexyl-P-phenylphosphonamidodiseleno-
ate) (3d): Yield 0.610 g (48%); pale-green paste. A pair of diastereo-
isomers was found in multinuclear NMR spectra in ca. 1:1 intensity
ratio. IR (KBr): ν = 1436 (m), 1396 (m), 1078 (s), 997 (m), 886 (m),
˜
746 (s), 688 (s), 572 (m), 519 (s), 485 (m) cm–1. 1H NMR (CD2Cl2):
δ = 7.98–7.96 (m, 2ϫ4 H, Ar-H), 7.47–7.42 (m, 2ϫ6 H, Ar-H),
3.96–3.79 (m, 2ϫ4 H, SeCH2), 2.81–1.15 (m, 2ϫ28 H, NH, cyclo-
hexyl-H) ppm. 13C NMR (CD2Cl2): δ = 137.1 (d, JP,C = 86.2 Hz),
1,2-Phenylenebis(methylene)
Bis(N-isopropyl-P-phenylphosphon-
amidodiselenoate) (3h): Yield 0.495 g (66%); pale-green paste. A
pair of diastereoisomers was found in multinuclear NMR spectra
in ca. 3:2 intensity ratio. IR (KBr): ν = 1434 (m), 1362 (m), 1124
˜
1
(m), 1096 (m), 1007 (s), 881 (s), 744 (s), 688 (s), 532 (s) cm–1. H
132.7 (d, JP,C = 3.1 Hz), 130.8 (d, JP,C = 12.5 Hz), 128.4 (d, JP,C
=
13.5 Hz), 52.9, 35.7, 33.4, 25.9, 25.1, 24.5 ppm. 31P NMR
(CD2Cl2): δ = 53.5 (s, JP,Se = 384 Hz, JP,Se = 789 Hz), 53.4 (s, JP,Se
= 386 Hz, JP,Se = 786 Hz) ppm. 77Se NMR (CD2Cl2): δ = 326.7 (d,
JP,Se = 386 Hz), 326.3 (d, JP,Se = 388 Hz), –105.0 (d, JP,Se = 789 Hz),
–105.2 (d, JP,Se = 786 Hz) ppm. MS (CI+): m/z = 789 [M + H]+.
HRMS (C|I+): calcd for C28H43N2PSe4 [M + H] 788.9562; found
788.9556.
NMR (CD2Cl2): δ = 8.04–7.94 (m, 2ϫ4 H, Ar-H), 7.52–7.47 (m,
2ϫ6 H, Ar-H), 7.15–7.06 (m, 2ϫ4 H, Ar-H), 4.27–4.20 (m, 2ϫ2
H, CH), 3.92–3.83 (m, 2ϫ4 H, SeCH2), 2.74–2.68 (m, 2ϫ2 H,
NH), 1.15–1.08 (m, 2ϫ12 H, CH3) ppm. 13C NMR (CD2Cl2): δ =
137.6, 137.1, 136.6, 135.8, 132.2 (d, JP,C = 3.1 Hz), 131.0 (d, JP,C
=
12.5 Hz), 130.9 (d, JP,C = 12.5 Hz), 128.6 (d, JP,C = 13.5 Hz), 127.8
(d, JP,C = 13.5 Hz), 46.3, 33.7, 24.9, 24.8 ppm. 31P NMR (CD2Cl2):
δ = 54.2 (s, JP,Se = 385 Hz, JP,Se = 786 Hz), 54.1 (s, JP,Se = 385 Hz,
1,2-Phenylenebis(methylene) Bis(N-cyclohexyl-P-phenylphosphon-
amidodiselenoate) (3e): Yield 0.642 g (77%); milky green solid. A
pair of diastereoisomers was found in multinuclear NMR spectra
JP,Se = 786 Hz) ppm. 77Se NMR (CD2Cl2): δ = 392.7 (d, JP,Se
=
385 Hz), 392.1 (d, JP,Se = 385 Hz), –99.5 (d, JP,Se = 786 Hz), –99.7
(d, JP,Se = 786 Hz) ppm. MS (CI+): m/z = 755 [M + H]+. HRMS
(C|I+): calcd for C26H35N2PSe4 [M + H] 692.8788; found 692.8779.
in ca. 1:1 intensity ratio. IR (KBr): ν = 1435 (m), 1401 (m), 1290
˜
(w), 1072 (m), 1076 (s), 993 (m), 877 (m), 745 (s), 688 (s), 567 (m),
1
519 (s), 489 (m), 436 (m) cm–1. H NMR (CD2Cl2): δ = 7.94–7.88 1,2-Phenylenebis(methylene)
Bis(N,N-diisobutyl-P-phenylphos-
(m, 2ϫ4 H, Ar-H), 7.38–7.22 (m, 2ϫ6 H, Ar-H), 7.21–6.99 (m,
2ϫ4 H, Ar-H), 4.38–4.18 (m, 2ϫ2 H, cyclohexyl-H), 3.11–2.76
(m, 2ϫ6 H, SeCH2, NH), 1.86–1.12 (m, 2ϫ20 H, cyclohexyl-
phonamidodiselenoate) (3i): Yield 0.475 g (53%); pale-green paste.
Four diastereoisomers were found in multinuclear NMR spectra in
ca. 1:1:3:3 intensity ratio. IR (KBr): ν = 1616 (w), 1509 (w), 1436
˜
H) ppm. 13C NMR (CD2Cl2): δ = 137.3, 136.6, 136.1, 132.0, 130.9, (m), 1396 (m), 1216 (s), 1138 (s), 1026 (m), 897 (s), 747 (m), 715
1
130.8, 128.6, 128.4, 127.8, 53.1, 52.7, 35.6, 33.8, 33.4, 25.4,
(m), 692 (s), 541 (s), 487 (m) cm–1. H NMR (CD2Cl2): δ = 8.09–
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
7

Job/Unit: O30860
/KAP1
Date: 23-09-13 17:45:29
Pages: 10
G. Hua, K. S. A. Arachchige, A. M. Z. Slawin, J. D. Woollins
FULL PAPER
7.97 (m, 4ϫ4 H, Ar-H), 7.47–7.38 (m, 4ϫ6 H, Ar-H), 7.15–7.04 3.1 Hz), 131.2, 131.0, 130.8, 130.4, 128.5, 128.4, 128.3, 127.9, 127.7,
(m, 4ϫ4 H, Ar-H), 4.30–3.80 (m, 4ϫ8 H, CH2), 2.96–2.82 (m,
4ϫ4 H, SeCH2), 1.91–1.81 (m, 4ϫ4 H, CH), 0.85–0.75 (m, 4ϫ24
127.6, 56.0, 55.9, 34.5, 31.4, 31.3 ppm. 31P NMR (CD2Cl2): δ =
46.0 (s, JP,Se = 376 Hz, JP,Se = 789 Hz), 45.9 (s, JP,Se = 378 Hz, JP,Se
H, CH3) ppm. 13C NMR (CD2Cl2): δ = 137.8, 137.5, 137.4, 136.7, = 786 Hz) ppm. 77Se NMR (CD2Cl2): δ = 438.8 (d, JP,Se = 378 Hz),
136.4, 136.0, 135.9, 135.1, 132.2, 132.1, 131.8, 131.7, 131.0, 130.8,
130.5, 128.4, 128.2, 127.6, 127.5, 55.5, 34.5, 34.3, 30.3, 27.0, 26.9,
20.5, 20.3 ppm. 31P NMR (CD2Cl2): δ = 77.1 (s, JP,Se = 386 Hz,
JP,Se = 792 Hz), 76.8 (s, JP,Se = 386 Hz, JP,Se = 794 Hz), 76.2 (s, JP,Se
438.1 (d, JP,Se = 376 Hz), –50.3 (d, JP,Se = 789 Hz), –50.4 (d, JP,Se
= 789 Hz) ppm. MS (CI+): m/z = 783 [M + H]+. HRMS (C|I+):
calcd for C28H39N2P2Se4 [M + H] 782.9257; found 782.9238.
1,2-Phenylenebis(methylene)
Bis(N-sec-butyl-P-phenylphosphon-
= 386 Hz, JP,Se = 794 Hz), 76.1 (s, JP,Se = 386 Hz, JP,Se
=
amidodiselenoate) (3m): Yield 0.420 g (54%); yellow paste. Four
diastereoisomers were found in multinuclear NMR spectra in ca.
792 Hz) ppm. 77Se NMR (CD2Cl2): δ = 357.1 (d, JP,Se = 386 Hz),
354.1 (d, JP,Se = 386 Hz), 350.5 (d, JP,Se = 386 Hz), 350.1 (d, JP,Se
= 386 Hz), –95.6 (d, JP,Se = 792 Hz), –96.7 (d, JP,Se = 794 Hz), –98.4
(d, JP,Se = 794 Hz), –99.1 (d, JP,Se = 792 Hz) ppm. MS (CI+): m/z
= 895 [M + H]+. HRMS (C|I+): calcd for C36H55N2PSe4 [M + H]
895.0520; found 895.0498.
1.0:1.0:1.2:1.0 intensity ratio. IR (KBr): ν = 1453 (m), 1434 (s),
˜
1398 (m), 1131 (m), 1096 (s), 1038 (m), 1007 (m), 949 (m), 852 (m),
744 (s), 688 (s), 534 (vs), 490 (m) cm–1. 1H NMR (CD2Cl2): δ =
8.15–7.90 (m, 4ϫ4 H, Ar-H), 7.56–7.30 (m, 4ϫ6 H, Ar-H), 7.27–
7.05 (m, 4ϫ4 H, Ar-H), 4.23–4.05 (m, 4ϫ4 H, SeCH2), 3.95–3.86
(m, 4ϫ2 H, CH), 2.69–2.66 (m, 4ϫ2 H, NH), 1.62–1.28 (m, 4ϫ4
H, CH2), 1.15–1.09 (m, 4ϫ6 H, CH3), 0.85–0.83 (m, 4ϫ6 H,
CH3) ppm. 13C NMR (CD2Cl2): δ = 137.6, 137.2, 136.5, 135.9,
133.3, 132.0, 131.7, 131.1, 130.9, 130.5, 128.6, 128.4, 127.8, 127.7,
51.3, 51.2, 33.9, 32.4, 31.5, 30.2, 22.0, 10.2 ppm. 31P NMR
(CD2Cl2): δ = 55.2 (s, JP,Se = 384 Hz, JP,Se = 789 Hz), 55.1 (s, JP,Se
= 384 Hz, JP,Se = 789 Hz), 54.8 (s, JP,Se = 384 Hz, JP,Se = 789 Hz),
54.7 (s, JP,Se = 387 Hz, JP,Se = 789 Hz) ppm. 77Se NMR (CD2Cl2):
δ = 395.9 (d, JP,Se = 384 Hz), 395.2 (d, JP,Se = 384 Hz), 394.8 (d,
JP,Se = 384 Hz), 391.4 (d, JP,Se = 387 Hz), –99.0 (d, JP,Se = 789 Hz),
–99.5 (d, JP,Se = 789 Hz), –101.1 (d, JP,Se = 789 Hz), –101.4 (d, JP,Se
= 789 Hz) ppm. MS (CI+): m/z = 783 [M + H]+. HRMS (C|I+):
calcd for C28H39N2P2Se4 [M + H] 782.9257; found 782.9249.
Biphenyl-4,4Ј-Diylbis(methylene)
Bis(N-isopropyl-P-phenylphos-
phonamidodiselenoate) (3j): Yield 0.445 g (54%); reddish yellow so-
lid. A pair of diastereoisomers was found in multinuclear NMR
spectra in ca. 1:2 intensity ratio. IR (KBr): ν = 1580 (w), 1495 (s),
˜
1433 (m), 1396 (s), 1160 (s), 1094 (s), 1002 (m), 814 (s), 741 (s), 687
(s), 508 (s), 486 (s), 409 (m) cm–1. 1H NMR (CD2Cl2): δ = 8.01–
7.93 (m, 2ϫ4 H, Ar-H), 7.45–7.29 (m, 2ϫ14 H, Ar-H), 4.20–4.17
(m, 2ϫ4 H, SeCH2), 3.91–3.78 (m, 2ϫ2 H, CH), 2.65–2.55 (m,
2ϫ2 H, NH), 1.30–1.11 (m, 2ϫ12 H, CH3) ppm. 13C NMR
(CD2Cl2): δ = 139.5, 139.4, 138.4, 137.6, 132.0, 131.0, 130.8, 130.0,
129.7, 129.5, 128.6, 128.4, 127.1, 126.9, 46.2, 35.7, 24.9 ppm. 31P
NMR (CD2Cl2): δ = 54.0 (s, JP,Se = 387 Hz, JP,Se = 789 Hz), 53.9
(s, JP,Se = 387 Hz, JP,Se = 789 Hz) ppm. 77Se NMR (CD2Cl2): δ =
408.5 (d, JP,Se = 386 Hz), 408.4 (d, JP,Se = 386 Hz), –99.1 (d, JP,Se
= 789 Hz), –99.3 (d, JP,Se = 789 Hz) ppm. MS (CI+): m/z = 831 [M
+ H]+. HRMS (C|I+): calcd for C32H39N2P2Se4 [M + H] 830.9257;
found 830.9254.
1,3-Phenylenebis(methylene)
Bis(N-sec-butyl-P-phenylphosphon-
amidodiselenoate) (3n): Yield 0.470 g (60%); yellow paste. Four dia-
stereoisomers were found in multinuclear NMR spectra in ca.
1.1:1.0:1.0:1.2 intensity ratio. IR (KBr): ν = 1602 (m), 1485 (m),
˜
1435 (s), 1396 (m), 1184 (m), 1133 (m), 1097 (s), 1038 (m), 1008
(m), 951 (m), 744 (s), 692 (vs), 535 (vs), 487 (m) cm–1. 1H NMR
(CD2Cl2): δ = 8.15–7.96 (m, 4ϫ4 H, Ar-H), 7.51–7.46 (m, 4ϫ6
H, Ar-H), 7.14–6.90 (m, 4ϫ4 H, Ar-H), 4.10–4.04 (m, 4ϫ4 H,
SeCH2), 3.82–3.61 (m, 4ϫ2 H, CH), 2.69–2.64 (m, 4ϫ2 H, NH),
1.45–1.38 (m, 4ϫ4 H, CH2), 1.19–1.10 (m, 4ϫ6 H, CH3), 0.98–
0.83 (m, 4ϫ6 H, CH3) ppm. 13C NMR (CD2Cl2): δ = 139.7, 138.7,
137.1, 135.9, 132.1, 131.1, 130.9, 130.2, 130.0, 129.8, 128.9, 128.6,
128.4, 128.0, 127.9, 127.6, 51.3, 51.1, 50.1, 36.1, 35.9, 32.4, 31.5,
28.0, 27.4, 22.0, 18.2, 10.2 ppm. 31P NMR (CD2Cl2): δ = 55.0 (s,
1,3-Phenylenebis(methylene)
amidodiselenoate) (3k): Yield 0.460 g (59%); pale-yellow paste.
Three diastereoisomers were found in multinuclear NMR spectra
in ca. 1:2:2 intensity ratio. IR (KBr): ν = 1602 (m), 1483 (m), 1435
Bis(N-tert-butyl-P-phenylphosphon-
˜
(s), 1364 (s), 1217 (s), 1209 (s), 1094 (s), 993 (s), 840 (m), 794 (m),
745 (m), 691 (s), 529 (vs), 429 (m) cm–1. H NMR (CD2Cl2): δ =
1
8.09–8.00 (m, 3ϫ4 H, Ar-H), 7.51–7.44 (m, 3ϫ6 H, Ar-H), 7.23–
7.07 (m, 3ϫ4 H, Ar-H), 4.26–4.09 (m, 3ϫ4 H, SeCH2), 2.78 (br.,
3ϫ2 H, NH), 1.30–1.21 (m, 3ϫ18 H, CH3) ppm. 13C NMR
(CD2Cl2): δ = 140.0, 139.7, 139.2, 139.0, 138.2, 137.9, 132.7, 132.2,
131.8, 131.1, 130.9, 130.5, 130.4, 130.3, 130.1, 129.9, 129.1, 128.9,
128.7, 128.5, 128.3, 128.2, 128.1, 127.9, 127.7, 56.0, 55.9, 31.4, 31.3,
JP,Se = 390 Hz, JP,Se = 789 Hz), 54.9 (s, JP,Se = 390 Hz, JP,Se
789 Hz), 54.6 (s, JP,Se = 390 Hz, JP,Se = 789 Hz), 54.5 (s, JP,Se
=
=
390 Hz, JP,Se = 789 Hz) ppm. 77Se NMR (CD2Cl2): δ = 406.4 (d,
JP,Se = 390 Hz), 406.2 (d, JP,Se = 390 Hz), 406.1 (d, JP,Se = 390 Hz),
405.7 (d, JP,Se = 390 Hz), –97.1 (d, JP,Se = 789 Hz), –97.5 (d, JP,Se
= 789 Hz), –99.1 (d, JP,Se = 789 Hz), –99.5 (d, JP,Se = 789 Hz) ppm.
MS (CI+): m/z = 783 [M + H]+. HRMS (C|I+): calcd for
C28H39N2P2Se4 [M + H] 782.9257; found 782.9246.
27.8 ppm. 31P NMR (CD2Cl2): δ = 46.1 (s, JP,Se = 374 Hz, JP,Se
794 Hz), 45.9 (s, JP,Se = 367 Hz, JP,Se = 789 Hz), 45.8 (s, JP,Se
=
=
377 Hz, JP,Se = 789 Hz) ppm. 77Se NMR (CD2Cl2): δ = 450.7 (d,
JP,Se = 374 Hz), 447.8 (d, JP,Se = 377 Hz), 447.2 (d, JP,Se = 367 Hz),
–49.2 (d, JP,Se = 789 Hz), –49.8 (d, JP,Se = 789 Hz), –50.4 (d, JP,Se
= 794 Hz) ppm. MS (CI+): m/z = 783 [M + H]+. HRMS (C|I+):
calcd for C28H39N2P2Se4 [M + H] 782.9257; found 782.9250.
Supporting Information (see footnote on the first page of this arti-
cle): Copies of the 1H and 13C NMR spectra of the new com-
pounds.
1,2-Phenylenebis(methylene)
amidodiselenoate) (3l): Yield 0.396 g (51%); greenish yellow solid.
Bis(N-tert-butyl-P-phenylphosphon-
A pair of diastereoisomers was found in multinuclear NMR spectra
Acknowledgments
in ca. 1:1 intensity ratio. IR (KBr): ν = 1434 (s), 1363 (s), 1217 (s),
˜
1194 (s), 1093 (s), 990 (s), 838 (m), 746 (m), 725 (m), 688 (s), 529
(vs), 485 (m), 432 (m) cm–1. 1H NMR (CD2Cl2): δ = 8.10–8.01 (m,
2ϫ4 H, Ar-H), 7.49–7.44 (m, 2ϫ6 H, Ar-H), 7.36–7.31 (m, 2ϫ2
H, Ar-H), 7.16–7.08 (m, 2ϫ2 H, Ar-H), 4.41–4.19 (m, 2ϫ4 H,
SeCH2), 2.83 (br., 2ϫ2 H, NH), 1.28 (s, 18 H, CH3), 1.26 (s, 18
H, CH3) ppm. 13C NMR (CD2Cl2): δ = 138.4 (d, JP,C = 109 Hz),
The authors are grateful to the University of St Andrews for finan-
cial support and the EPSRC National Mass Spectrometry Service
Centre (Swansea) for mass spectral measurements.
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137.3 (d, JP,C = 108 Hz), 133.3 (d, JP,C = 3.1 Hz), 131.8 (d, JP,C
=
8
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Organophosphorus-Selenium Heteroatom Derivatives
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Received: June 12, 2013
Published Online: ᭿
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9

Job/Unit: O30860
/KAP1
Date: 23-09-13 17:45:29
Pages: 10
G. Hua, K. S. A. Arachchige, A. M. Z. Slawin, J. D. Woollins
FULL PAPER
Phosphorus Selenium Chemistry
G. Hua, K. S. A. Arachchige,
A. M. Z. Slawin, J. D. Woollins* .... 1–10
Organophosphorus-Selenium Heteroatom
Derivatives from Selenation of Primary/
Secondary Amines and Haloalkanes/Di-
haloalkanes
Keywords: Woollins’ reagent / Selenium /
Phosphorus / Amines / Haloalkanes
Woollins’ reagent has been applied as a
highly efficient building block for the syn-
thesis of organo selenium-phosphorus
heteroatom compounds.
10
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