New routes to β-iminophosphonates, phosphineoxides, and sulfides

Article abstract of DOI:10.1080/10426507.2010.527877

Two synthetic methods leading to β-iminophosphonates, phosphineoxides, and sulfides 2 are reported. The first method involves the reaction of imines with chlorophosphines and phosphites followed by oxidation or sulfurization. The second one utilizes the r

Full text of DOI:10.1080/10426507.2010.527877

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New Routes to β-Iminophosphonates,
Phosphineoxides, and Sulfides
Hosni Slimani a & Soufiane Touil a
a Laboratoire de Chimie Organique des Hétéroéléments,
Département de Chimie, Faculté des Sciences de Bizerte, Jarzouna,
Tunisie
Published online: 11 Aug 2011.
To cite this article: Hosni Slimani & Soufiane Touil (2011) New Routes to β-Iminophosphonates,
Phosphineoxides, and Sulfides, Phosphorus, Sulfur, and Silicon and the Related Elements, 186:8,
1655-1664, DOI: 10.1080/10426507.2010.527877
To link to this article: http://dx.doi.org/10.1080/10426507.2010.527877
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Phosphorus, Sulfur, and Silicon, 186:1655–1664, 2011
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2010.527877
NEW ROUTES TO β-IMINOPHOSPHONATES,
PHOSPHINEOXIDES, AND SULFIDES
Hosni Slimani and Soufiane Touil
Laboratoire de Chimie Organique des He´te´roe´le´ments, De´partement de Chimie,
Faculte´ des Sciences de Bizerte, Jarzouna, Tunisie
GRAPHICAL ABSTRACT
Abstract Two synthetic methods leading to β-iminophosphonates, phosphineoxides, and sul-
fides 2 are reported. The first method involves the reaction of imines with chlorophosphines and
phosphites followed by oxidation or sulfurization. The second one utilizes the reaction of imines
with diethylchlorophosphate and thiophosphate. The stereochemistry of the obtained products
is discussed, and their structure is confirmed by NMR (1H, 31P, 13C) and IR spectroscopies,
and by mass spectrometry.
Supplemental materials are available for this article. Go to the publisher’s online edition of
Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.
Keywords
Imines; β-iminophosphineoxides; β-iminophosphinesulfides; β-imino-
phosphonates
INTRODUCTION
An increasing interest has been paid for several years to the synthesis of β-
iminophosphonates.1–6 Such interest has been stimulated by their utility as key intermediates
Received 8 May 2010; accepted 26 September 2010.
Address correspondence to Pr. Soufiane Touil, Laboratoire de Chimie Organique des He´te´roe´le´ments,
De´partement de Chimie, Faculte´ des Sciences de Bizerte, 7021-Jarzouna, Tunisie. E-mail: soufiane.touil@fsb.
rnu.tn
1655

1656
H. SLIMANI AND S. TOUIL
in the synthesis of β-aminophosphonates,1–5,7 which are known for their interesting biologi-
cal activities as antibacterial agents,8 enzyme inhibitors,9 haptens for catalytic antibodies,10
and anti-HIV agents.11
β-Iminophosphonates are commonly obtained by the reaction of amines with β-
ketophosphonates, which are difficult to synthesize.4,6,12 Another approach,13–17 but leading
to β-iminophosphines, involves the reaction of lithium salts of imines with chlorophos-
phines. The phosphorus(III) derivatives obtained are unstable and cannot be widely used in
further syntheses. Also, the reaction is limited by a competitive N-phosphorylation process
affording N-phosphorus-substituted enamines.
This prompted us to develop new, simple, one-pot methodologies for the synthesis
of β-iminophosphonates, phosphineoxides, and sulfides, which use easily made imines
directly, instead of their lithium salts, and commercially available chlorophosphines, phos-
phites, or phosphates as starting materials. These new syntheses have the advantages of
good yields, stable products, and mild reaction conditions; besides no competitive N-
phosphorylation process was observed in all cases.
RESULTS AND DISCUSSION
For the synthesis of β-iminophosphonates, phosphineoxides, and sulfides 2, we have
used two different approches. The first one (Method A) involves the reaction of imines
with chlorophosphines and phosphites followed by oxidation or sulfurization. The sec-
ond method (Method B) utilizes the reaction of imines with diethylchlorophosphate and
thiophosphate.
Method A: Reaction of Imines with Chlorophosphines and Phosphites
Treatment of imines 1 with chlorophosphines and phosphites, performed in acetoni-
trile at 0◦C in the presence of an equimolar amount of triethylamine, led to the formation of
the phosphine intermediate I (Scheme 1). A subsequent oxidation or sulfurization carried
out, in a one-pot reaction, by treating respectively with dimethylsulfoxide (DMSO) under
reflux or with elemental sulfur at 40◦C, furnished the β-iminophosphonates, phosphineox-
ides, and sulfides 2 in good yields.
Based on some data in the literature18 concerning the reactivity of imines with
electrophilic agents, we can propose the reaction mechanism of Scheme 1, which involves
a six-membered cyclic transition state TS. This allows the hydrogen on the nitrogen atom
to be transferred concertedly and avoids the formation of charged intermediates that are
high in energy.
In order to obtain a better perspective on the reaction mechanism, we carried out a
theoretical ab initio SCF/6-31G calculation, which established that the reaction proceeds
through a six-membered cyclic transition state having a compact structure stabilized by
MO interactions (Figure 1).
Method B: Reaction of Imines with Diethylchlorophosphate
and Thiophosphate
Similar to the reaction of chlorophosphines and phosphites, we found that
chlorophosphates and thiophosphates can also react with imines 1 in the presence of

β-IMINOPHOSPHONATES, PHOSPHINEOXIDES, AND SULFIDES
1657
Scheme 1
an equimolar amount of triethylamine and using diethylether as solvent to afford the
β-iminophosphonates and phosphinesulfides 2 in good yields (Scheme 2).
It is important to note that all compounds 2, synthesized by methods A and B, are
obtained exclusively in their imine form. Indeed, the reaction did not afford any identifiable
enamine tautomer for compounds 2, as evidenced by spectroscopic data.

1658
H. SLIMANI AND S. TOUIL
Figure 1 Calculated transition state TS in the formation of compound 2a.
Spectrographic Study
Compounds 2 were characterized on the basis of their 31P, H, and 13C NMR data,
1
which indicate that they are obtained, in some cases, as a mixture of Z and E isomers
(Scheme 3). Their relative proportions were estimated from the 31P NMR spectra where a
singlet for each isomer is present (Table 1).
It is important to note here that the reaction shows considerable diastereoselectivity.
Indeed, the less hindered E isomer is the major or the sole one.
The Z and E configurations were attributed on the basis of C1 chemical shift values
(Table 2). Indeed, according to some data in the literature19–22 concerning the stereochem-
istry of imines, hydrazones, and oximes, the carbon adjacent to the C N double bond
Table 1 δ 31P in ppm and% of Z and E isomers for compounds 2
2a
2b
2c
2d
2e
2f
2g
δ
δ
31P(E)
31P(Z)
21.3
—
100
—
2.6
3.8
81
68.4
70.0
85
60.7
—
100
—
23.5
—
100
—
57.1
70.6
69
10.1
—
100
—
% E
% Z
19
15
31
2h
2i
2j
2k
2l
2m
2n
δ
δ
31P(E)
31P(Z)
59.6
—
100
—
70.3
—
100
—
8.9
—
100
—
21.3
—
100
—
9.8
—
100
—
9.9
—
100
—
67.6
71.6
62
% E
% Z
38

β-IMINOPHOSPHONATES, PHOSPHINEOXIDES, AND SULFIDES
1659
Scheme 2
Scheme 3

1660
H. SLIMANI AND S. TOUIL
Table 2 13C NMR for compounds 2: δ in ppm (JCP in Hz)
11
3
4
R1: C6H5 , CH2-CH3 ,
4
3
3
5
6
5
4
R2
X
CH2-CH2-CH2-CH2 , CH2-CH2-CH2
R2: H
2
C
1
R1
CH P(R4 )2
8
CH3
11
11
7
7
R3: C6H5 , CH2-C6H5 , CH
N
R3
CH3
10
9
11
R4: CH3-CH2-O , C6H5
2
2a
2b
2c
2d
2e
2f
2g
C1
C2
C3
C4
C5
26.1 (71.6) 20.8 (52.1;Z) 39.8 (44.3;Z) 44.4 (71.0) 30,7 (38.6) 63.3 (99.6;Z) 42.3 (109.4)
45.5 (67.9;E) 46.5 (70.9;E)
63.4 (98.9;E)
162.8 (Z)
160.2 (E)
33.7 (Z)
32.7 (E)
22.7 (Z)
23.1 (E)
30.3 (Z)
28.6 (E)
—
141.1
—
151.3 (Z)
154.7 (E)
—
150.7 (Z)
157.8 (E)
—
145.0
45.3
8.1
142.7
45.0
7.8
157.4
36.3 (18.1)
19.4
—
—
—
—
—
—
—
—
23.4
C6
C7
—
—
—
—
—
42.5
—
42.4
—
42.8
39.4 (Z)
42.6 (E)
—
45.5
43.4
C8
C9
—
—
—
—
—
—
—
—
—
60.3 (6.0)
65.0 (3.0;Z) 62,9 (4.5;Z)
62.4 (4.5;E) 66.2 (3.8;E)
15.5 (8.3;Z) 16.0 (8.3;Z)
15.9 (7.5;E) 15.7 (7.5;E)
62.6 (4.5; Z)
61.5 (6.0; E)
15.7 (7.5; Z)
16.2 (8.3; E)
C10
—
—
—
14.3 (6.8)
C11 127.7–137.8∗ 117.4–133.0 117.3–137.5 127.0–137.6 127.1–136.6 125.1–135.1 124.0–131.9
2h
2i
2j
2k
2l
2m
2n
C1
C2
C3
C4
51.6 (92.1)
143.8
44.2 (126.0) 54.6 (184.0) 73.9 (81.7) 33.5 (123.8) 43.9 (67.2) 41.0 (125.7;Z)
57.0 (172.7;E)
136.6
42.6 (14.3)
24.3
140.4
41.2 (18.1)
24.5
136.4
30.9 (4.7)
25.0
168.6
46.0
8.5
155.9
158.0 (Z)
152.6 (E)
41.5 (15.8;Z)
29.0 (9.8;E)
23.7 (Z)
42.2 (18.0)
23.9
—
—
24.4 (E)
C5
C6
36.1 (15.5)
27.2
24.1 (14.3)
25.0
25.7 (18.1)
25.6
20.1 (9.7)
27.0
—
—
—
—
26.1 (6.8)
27.6 (Z)
27.3 (E)
C7
45.1
40.9
44.7
42.0
44.8
41.6
45.1 (Z)
45.7 (E)
C8
C9
—
—
26.0
61.5 (5.3)
—
61.2 (6.0)
—
—
—
61.8 (5.3)
—
60.4 (5.3)
—
62.1 (5.3;Z)
65.7 (6.8;E)
15.5 (8.3;Z)
15.2 (8.0;E)
C10
—
14.9 (6.8)
—
15.7 (7.5)
—
15.7 (8.3)
14.4 (9.8)
C11 127.5–134.4
126.0–129.1 127.5–132.6 123.4–129.8 124.2–131.7 124.8–131.1
∗For aromatic 13C NMR individual signals, see the Experimental section.

β-IMINOPHOSPHONATES, PHOSPHINEOXIDES, AND SULFIDES
1661
resonates at a higher field when it is in syn position to the group on nitrogen atom (R3 in
our case).
EXPERIMENTAL
1H, 31P, and 13C NMR spectra were recorded with CDCl3 as solvent on a Bruker-300
spectrometer. The chemical shifts are reported in ppm relative to TMS (internal reference)
1
for H and 13C NMR and relative to 85% H3PO4 (external reference) for 31P NMR. The
1
coupling constants are reported in Hz. For the H NMR, the multiplicities of signals are
indicated by the following abbreviations: s: singlet, d: doublet, t: triplet, q: quartet, qp:
quintet, m: multiplet.
Mass spectra were determined on a Micromass Quatro-ultima Pt (triple quadrupole)
spectrometer under electrospray ionization (ESI) conditions, or on a GCMSD 5975B (Ag-
ilent technologies) spectrometer under electronic impact ionization (EI) conditions.
IR spectra were recorded in CHCl3, on a Perkin Elmer Paragon 1000 PC spectrometer.
The progress of the reactions was controlled by TLC. Purification of products was performed
by column chromatography using silica gel 60 (Fluka).
Synthesis of Imines 1
The starting imines 1 were prepared according to reported procedures.23–25
Synthesis of β-Iminophosphonates, Phosphineoxides, and Sulfides 2
Method A. To a mixture of imine 1 (0.01 mol), triethylamine (0.012 mol), and dry
MeCN (50 mL), cooled at 0◦C and maintained under a nitrogen atmosphere, a solution of
chlorophosphine or phosphite (0.01 mol) in dry MeCN (30 mL) was added dropwise with
stirring. Stirring at 0◦C was continued for 1 h. The reaction mixture was then treated with
DMSO or sulfur as follows:
Oxidation. DMSO (0.01 mol) was added, and the mixture was heated under reflux
for 2 h. After cooling, CHCl3 (50 mL) was added. The organic phase was washed with
water (2 × 25 mL), dried over Na2SO4, and concentrated in vacuo. The residue obtained
was chromatographed on a silica gel column using ether as eluent.
Sulfurization. Sulfur (0.01 mol) was added, and the mixture was heated at 40◦C
for 30 min. After cooling, CHCl3 (50 mL) was added. The organic phase was washed with
water (2 × 25 mL), dried over Na2SO4, and concentrated in vacuo. The residue obtained
was chromatographed on a silica gel column using ether as eluent.
Method B. To a mixture of imine 1 (0.01 mol), triethylamine (0.012 mol), and
dry Et2O (50 mL), cooled at 0◦C and maintained under a nitrogen atmosphere, a solution
of diethylchlorophosphate or thiophosphate (0.01 mol) in dry Et2O (10 mL) was added
dropwise with stirring. Stirring was continued for 24 h at 25◦C. The reaction mixture was
then extracted with water (2 × 25 mL). The organic phase was dried over Na2SO4 and
concentrated in vacuo. The residue obtained was chromatographed on a silica gel column
using ether as eluent.
2a: mp = 265◦C; 1H NMR: δ = 1.79 (d, 2H, 2JPH = 13.6, CH2-P O); 3.56 (s, 2H,
N-CH2-Ph); 7.11-7.97(m, 20H, H arom); IR: νC N = 1656 cm−1; νP O = 1252 cm−1
;
13C
NMR for arom-C: δ = 127.7, 127.9, 128.1, 128.2, 128.3, 128.6, 128.7, 129.0, 130.4, 130.6,
130.8, 131.1, 131.2, 132.5, 136.0, 137.8; ESI-MS: m/z = 427.552([M+NH4]+).

1662
H. SLIMANI AND S. TOUIL
2b: Oil; 1H NMR: δ = 1.04 (t, 6H, 3JHH = 6.0, CH3-CH2-O;E); 1.14(t, 6H, 3JHH
=
2
2
6.0, CH3-CH2-O;Z); 2.12 (d, 2H, JPH = 25.0, CH2-P O;Z); 2.33(d, 2H, JPH = 15.0,
3
3
3
CH2-P O;Z); 3.88 (qp, 4H; JHH = JPH = 6.0, CH3-CH2-O;E); 4.04 (qp, 4H, JHH
3JPH = 6.0, CH3-CH2-O;Z); 6.50–7.80 (m, 10H, H arom); IR: νC N = 1642 cm−1; νP
=
=
O
1266 cm−1
;
13C NMR for arom-C: δ = 117.4, 119.5, 121.0, 123.7, 127.8, 128.0, 128.1,
128.3, 128.4, 128.7, 129.1, 129.3, 132.4, 133.0; ESI-MS: m/z = 349.428([M+NH4]+).
2c: Oil; 1H NMR: δ = 1.10 (t, 6H, 3JHH = 6.0, CH3-CH2-O;Z); 1.17 (t, 6H, 3JHH
=
6.0, CH3-CH2-O,E); 1.28 (d, 2H, 2JPH = 9.0, CH2-P = S, E); 1.60 (d, 2H, 2JPH = 9.0, CH2-
3
3
3
3
P S,Z); 3.92 (qp, 4H, JHH = JPH = 6.0, CH3-CH2-O,Z); 4.06 (qp, 4H, JHH = JPH
=
6.0, CH3-CH2-O,E); 6.21 (s, 2H, Ph-CH2,Z); 6.23 (s, 2H, Ph-CH2,E); 6.99–7.73 (m, 10H,
H arom); IR: νC = 1610 cm−1; νP = 1100 cm−1
;
13C NMR for arom-C: δ = 117.3,
N
S
125.5, 125.7, 125.9, 126.0, 126.9, 127.4, 127.6, 128.1, 128.7, 129.2, 130.9, 137.3, 137.5;
EI-MS: m/z = 361(M+, 15%); 345(30%); 332(16%); 270(60%); 91(100%); 77(28%).
2d: Oil; 1H NMR: δ = 1.19 (t, 3H, 3JHH = 7.0, CH3-CH2); 2.05 (d, 2H, 2JPH = 35.7,
CH2-P S); 3.04 (q, 2H, 3JHH = 7.0, CH3-CH2); 3.64 (s, 2H, Ph-CH2); 6.92–8.16 (m, 15H,
H arom). IR: νC = 1645 cm−1; νP = 1111 cm−1
;
13C NMR for arom-C: δ = 127.0,
N
S
127.2, 127.3, 127.6, 128.5, 128.7, 130.2, 130.3, 131.2, 132.8, 136.5, 137.6; EI-MS: m/z =
377(M+, 8%); 286(10%); 217(10%); 160(66%); 91(100%); 77(20%).
2e: Mp = 138◦C; 1H NMR: δ = 1.28 (t, 3H, 3JHH = 6.6, CH3-CH2); 2.22 (d, 2H, 2JPH
=
3
47.1, CH2-P O); 3.02 (q, 2H, JHH = 6.6, CH3-CH2); 3.66 (s, 2H, Ph-CH2); 7.14–7.54
(m, 15H, H arom). IR: νC N = 1646 cm−1; νP O = 1260 cm−1
;
13C NMR for arom-C: δ =
127.1, 127.3, 127.6, 127.7, 127.9, 128.1, 128.2, 128.9, 129.7, 131.2, 134.8, 136.6; EI-MS:
m/z = 361(M+, 33%); 270(13%); 201(53%); 160(86%); 91(100%); 77(29%).
2f: Oil; 1H NMR: δ = 1.08 (t, 6H, 3JHH = 6.0, CH3-CH2-O, Z); 1.19 (t, 6H, 3JHH
=
6.0, CH3-CH2-O, E); 1.25–3.05 (m, 7H, cyclic H and CH-P S); 3.79–4.15 (m, 6H, CH3-
CH2-O and Ph-CH2); 6.94–7.31 (m, 5H, H arom); IR: νC = 1616 cm−1; νP = 1096
N
S
cm−1
;
13C NMR for arom-C: δ = 125.1, 125.7, 127.0, 127.7, 128.2, 128.4, 132.9, 135.1;
EI-MS: m/z = 325(M+, 25%); 234(16%); 186(60%); 91(100%).
1
3
2g: Oil; H NMR: δ = 1.22 (t, 6H, JHH = 6.0; CH3-CH2-O); 1.39–3.20 (m, 7H,
cyclic H and CH-P O); 3.98–4.30 (m, 6H, CH3-CH2-O and Ph-CH2); 7.00–7.60 (m, 5H,
H arom); IR: νC = 1620 cm−1; νP = 1250 cm−1
;
13C NMR for arom-C: δ = 124.0,
N
O
125.2, 126.8, 131.9; EI-MS: m/z = 309(M+, 33%); 218(20%); 186(67%); 91(100%).
1
2h: Oil; H NMR: δ = 1.50–3.10 (m, 9H, cyclic H and CH-P S); 4.10 (s, 2H,
Ph-CH2); 6.90–8.20 (m, 15H, H arom). IR: νC = 1650 cm−1; νP = 1106 cm−1
;
13C
N
S
NMR for arom-C: δ = 127.5, 127.6, 128.0, 128.4, 128.5, 128.6, 128.7, 131.5, 131.6, 132.0,
133.1, 134.4; EI-MS: m/z = 403(M+, 16%); 312(20%); 217(29%); 186(75%); 91(100%);
77(25%).
1
3
3
2i: Oil; H NMR: δ = 1.07 (d, 6H, JHH = 6.0, CH3-CH-N); 1.22 (t, 6H, JHH
=
3
6.0, CH3-CH2-O); 1.38–2.25 (m, 9H, cyclic H and CH-P S); 3.36 (m, 1H, JHH = 6.0,
CH3-CH-N); 3.88–4.10 (m, 4H, CH3-CH2-O); IR: νC N = 1632 cm−1; νP S = 1097 cm−1
ESI-MS: m/z = 292.474([M+H]+).
;
1
3
2j: Oil; H NMR: δ = 1.18 (t, 6H, JHH = 7.2, CH3-CH2-O); 1.53–2.28 (m, 9H,
cyclic H and CH-P O); 3.80–4.05 (m, 6H, CH3-CH2-O and Ph-CH2); 7.04–7.30 (m, 5H,
H arom); IR: νC = 1631 cm−1; νP = 1254 cm−1
;
13C NMR for arom-C: δ = 126.0,
N
O
126.7, 127.8, 129.1; EI-MS: m/z = 323(M+, 36%); 232(15%); 186(62%); 91(100%).
2k: Mp = 176◦C; 1H NMR: δ = 1.50–2.50 (m, 9H, cyclic H and CH-P O); 5.52 (m,
2H, Ph-CH2); 7.00–8.30 (m, 15H, H arom); IR: νC N = 1664 cm−1; νP O = 1253 cm−1
;
13C
NMR for arom-C: δ = 127.5, 127.6, 127.9, 128.2, 128.4, 128.8, 129.0, 130.0, 130.8, 131.8,

β-IMINOPHOSPHONATES, PHOSPHINEOXIDES, AND SULFIDES
1663
132.5, 132.6; EI-MS: m/z = 387(M+, 19%); 296(71%); 201(63%); 186(90%); 91(100%);
77(28%).
1
3
3
2l: Oil; H NMR: δ = 1.15 (t, 3H, JHH = 6.0, CH3-CH2-C); 1.25 (t, 6H, JHH
=
2
3
6.0; CH3-CH2-O); 2.18 (d, 2H, JPH = 21.0, CH2-P O); 3.02 (q, 2H, JHH = 6.0, CH3-
CH2-C); 3.84–4.16 (m, 6H, CH3-CH2-O and Ph-CH2); 7.00–7.62 (m, 5H, H arom). IR:
νC
= 1651 cm−1; νP
= 1265 cm−1
;
13C NMR for arom-C: δ = 123.4, 125.2,
N
O
128.6, 129.8; EI-MS: m/z = 297(M+, 14%); 281(34%); 268(16%); 207(67%); 91(100%);
77(17%).
2m: Oil; 1H NMR: δ = 1.24 (t, 6H, 3JHH = 6.0, CH3-CH2-O); 2.35 (d, 2H, 2JPH
=
30.0, CH2-P O); 3.85–4.30 (m, 6H, CH3-CH2-O and Ph-CH2); 6.80–8.20 (m, 10H, H
arom); IR: νC = 1630 cm−1; νP = 1274 cm−1
;
13C NMR for arom-C: δ = 124.2,
N
O
124.6, 125.1, 126.9, 127.4, 127.7, 128.0, 131.5, 131.7; EI-MS: m/z = 345(M+, 20%);
329(15%); 254(60%); 91(100%); 77(20%).
2n: Oil; 1H NMR: δ = 1.14(t, 6H, 3JHH = 6.0, CH3-CH2-O, Z); 1.25 (t, 6H, 3JHH
=
6.0, CH3-CH2-O, E); 1.45–3.01 (m, 9H, cyclic H and CH-P S); 3.84–4.19 (m, 6H, CH3-
CH2-O and Ph-CH2); 7.00–7.57 (m, 5H, H arom); IR: νC = 1631 cm−1; νP = 1096
N
S
cm−1
;
13C NMR for arom-C: δ = 124.8, 126.3, 126.7, 127.2, 127.9, 128.3, 130.4, 131.1;
EI-MS: m/z = 339(M+, 30%); 248(12%); 186(55%); 91(100%).
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