5-phosphorylated 1,2-Disubstituted imidazoles

Article abstract of DOI:10.1002/hc.20550

1,2-Disubstituted imidazoles react with phosphorus(III) halides in pyridine regioselectively at position 5. The reaction proceeds the more readily, the higher the electron-donating ability of the 2-substituent in the starting imidazole. Hitherto unknown d

Full text of DOI:10.1002/hc.20550

Heteroatom Chemistry
Volume 20, Number 5, 2009
5-Phosphorylated 1,2-Disubstituted
Imidazoles
A. A. Yurchenko, A. N. Huryeva, E. V. Zarudnitskii, A. P. Marchenko,
G. N. Koidan, and A. M. Pinchuk
Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Murmanskaya Str. 5,
Kiev-94, 02094, Ukraine
Received 6 April 2009; revised 28 July 2009
The compounds concerned are studied for about
ABSTRACT: 1,2-Disubstituted imidazoles react
two decades, and a series of synthetic approaches
with phosphorus(III) halides in pyridine regiose-
are currently available to obtain imidazolylphos-
lectively at position 5. The reaction proceeds the
phonates and tertiary phosphines as, for instance,
more readily, the higher the electron-donating abil-
the Pd-catalyzed reaction of 4(5)-imidazolyl bro-
ity of the 2-substituent in the starting imidazole.
mides or iodides with phosphites [3,6], cyclization
Hitherto unknown dihalo(imidazol-5-yl)phosphines
of functionalized phosphonates [8–10], condensa-
have been obtained, and their properties have been
tion of diethyl(2,2-dichloro-1-isocyanoethenyl)phos-
studied. Also synthetic methods for the preparation
phonate [11] or diethyl α-aminocyanomethyl-
of various monohalo(organyl)(imidazolyl)phosphines
phosphonate [4] with primary amines, and the
ꢀ
C
have been developed.
2009 Wiley Periodicals, Inc.
reaction of Li and Mg derivatives of disubstituted
imidazoles with phosphorus acid chlorides [5,7,12].
However, some key functional compounds such
as imidazol-4(5)-yl-halo- or dihalophosphines re-
mained unknown until our research.
Heteroatom Chem 20:289–308, 2009; Published online
in Wiley InterScience (www.interscience.wiley.com). DOI
10.1002/hc.20550
As previously reported, 1,3-azoles can be directly
C-phosphorylated with phosphorus(III) halides in
pyridine in the presence of Et3N [13]. Under
such conditions, 1-alkylimidazoles readily react
with PHal3 to give 2-phosphorylated products [14],
whereas 1-aryl-2-methylimidazoles undergo phos-
phorylation at the methyl group [15]. The lat-
ter work also included reaction of 1-methyl-2-
methylthioimidazole with PCl3 at position 5, though
only the 31P NMR characterization data for the final
product is present.
Here we address phosphorylation of 1,2-
disubstituted imidazoles with phosphorus(III)
halides focusing on the features that influence
the readiness of the reaction. The objective of the
study is 1-methyl-2-R-substituted imidazoles 1a–c
with the 2-substituent sterically and electronically
varied (R = NMe2 (a), SMe (b), Ph (c)). As phos-
phorylating agents, we used phosphorus trihalides
INTRODUCTION
C-Phosphorylated imidazoles have attracted con-
siderable pharmaceutical and synthetic interest be-
cause a number of them are remarkable for their
high biological activity and also represent promis-
ing ligands for metal complex catalysis [1,2]. More-
over, 4(5)-phosphorylated imidazole derivatives can
serve as reactants for the synthesis of phosphorus-
containing purine analogues [3,4] and function as
ligands in metalloenzymes [5], selective inhibitors
of nucleoside deaminases, glycosyl- and acetyltrans-
ferases [6,7], and neuromediator antagonists [8] in
metabolic regulation.
Phosphorylated Azoles. Part IV.
Correspondence to: Aleksandr A. Yurchenko; e-mail:
yurchenko@ioch.kiev.ua.
c
ꢀ
2009 Wiley Periodicals, Inc.
289

290 Yurchenko et al.
TABLE 1 Reaction Conditions for the Synthesis Of Phos-
phines 7a–c by Phosphorylation with Ph2PHal
acceptor, it is possible to suppress tar formation and
to increase target product yields (e.g., from 49% to
92% for dichloride 2a). Although the reaction is gen-
erally performed with 2 equiv of imidazoles 1a–c, a
two- to three-fold PHal3 excess is needed for only
monohalo substitution to occur. It is noteworthy
that on longer heating at 120◦C, imidazole 1c reacts
with PCl3 in a 1:1 ratio, with HCl finally captured by
pyridine.
NMe2 (a)
Ph2PCl
20◦C
SMe (b)
Ph2PBr
30◦C
Ph (c)
Ph2PBr
100◦C
20◦C
Reaction time
Yield (%)
22 h
84
8 days
70
54 h
54
–
–
The most reactive is imidazole 1a bearing a
strong electron-donating NMe2 group at position 2;
its reaction with PCl3 is complete at 20◦C within 2 h.
Compounds 1b,c containing less electron-donating
2-substituents, the SMe and Ph groups, respectively,
are phosphorylated with PCl3 very slowly at 20◦C but,
if heated to 100◦C, the reaction is completed within
3 h for 1b and 48 h for 1c. The heating of 1b at 100◦C
for more than 3 h is useless because under these con-
ditions imidazole hydrochloride can be dealkylated
[16], thus leading to SH-phosphorylation and hence
to a mixture of products. It has been found that it
is conveniently to prepare phosphonous dichlorides
using Cl2PBr (a mixture of PCl3 and PBr3 in 2n:1
ratio, where n ≥ 1); in this case (method B), the re-
action with 1c is completed at 120◦C within 2 h. A
stronger phosphorylating agent, PBr3, reacts with 1c
at 20◦C within 8 days to afford phosphonous dibro-
mide 2d. Compounds 2a–d appear as pale yellow vis-
cous liquids most readily hydrolyzed by atmospheric
moisture and can be distilled in vacuo without de-
composition (Table 2).
PHal3 (Hal Cl; Br; see Table 1), easily available
functionalized dihalophosphines RPHal2 (R Ph;
CCl3; CCl2 CCl, Me2N), and diphenylhalo+ Ph2PHal
(Hal Cl; Br).
RESULTS AND DISCUSSION
Phosphorylation with Phosphorus(III) Halides:
Synthesis of Imidazol-5-yl-phosphonous
Dihalides
As it was found that imidazoles 1a–c reacted with
PHal3 in pyridine in a 2:1 ratio to give imidazol-5-yl-
phosphonous dihalides 2a–d (Scheme 1). Among the
peculiarities of this reaction, we note that the pres-
ence of triethylamine leads to tar formation and an
increased amount of by-products, unlike the analo-
gous phosphorylation of 1,3-azoles [13,14]. With a
stronger base, diisopropylethylamine, the reaction
proceeds likewise so that the target phosphorylated
products cannot be detected even spectroscopically.
Using the starting imidazole as a hydrogen chloride
Like arylphosphonous dihalides, dihalides 2a–
d actively react with N-, O-, and C-nucleophiles
N
N
CF3CCl2
Cl
i
NMe2
NMe2
P
P
N
N
Me2N
Me2N
Me
Me
5
4
Me3SiNMe2
N
N
N
PHal3 or [Cl2PBr]
4 Alk2NH
R
(Alk2N)2P
Hal2P
R
R
N
Py
N
N
Me
1a–c
Me
3a–d
Me
2a–d
2 i-PrOH/ Et3N
2 PhLi
N
1–7:R = NMe2 (a); SMe (b); Ph (c,d)
2: Hal = Cl (a–c); Br (d)
3: Alk = Et (a–c); Me (d)
N
N
(i-PrO)2P
R
Ph2P
Ph
i = F3CCCl3 / (Et2N)3P
N
Me
6a,b
Me
7c
SCHEME 1
Heteroatom Chemistry DOI 10.1002/hc

5-Phosphorylated 1,2-Disubstituted Imidazoles 291
TABLE 2 Physical and Analytical Data of 5-Phosphorylated 1,2-Disubstituted Imidazoles
Found (Calcd) (%)
Mp (◦C) (Cryst. solvent)
Bp/pressure, (◦C)/Torr
Molecular
Formula
Compound
Yield (%)
N
P
2a
2b
2c
2d
3a
3b
3c
3d
4
5
6a
6b
7a
7b
7c
8a
92
90
62
64
53
48
54
75
83
73
76
82
84
42
54
56
91
95
83
73
66
44
48
66
71
48
91
31
25
26
77
44
76
66
36
46
11
90
67
60
7
70
85
97
65
33
44
45
55
35
61
76
86
50
40
87
80
55
83–85/0.02
67–69; 104–106/0.02
145–150/0.05
186–190/0.05
154–156/0.03
136–139/0.02
135–140/0.02
140–141/0.02
110–120/0.05
64–66 (pentane)
106–107/0.02
94–95/0.02
C6H10Cl2N3P
C5H7Cl2N2PS
C10H9Cl2N2P
C10H9Br2N2P
C14H30N5P
C13H27N4PS
C18H29N4P
C14H21N4P
C8H16ClN4P
C10H16Cl2F3N4P
C12H24N3O2P
C11H21N2O2PS
C18H20N3P
C17H17N2PS
C22H19N2P
C14H30N5PS
C13H27N4PS2
18.77 (18.59)
12.04 (12.23)
10.55 (10.81)
8.01 (8.06)
23.15 (23.39)
18.68 (18.53)
16.67 (16.85)
20.20 (20.28)
23.84 (23.88)
15.90 (15.96)
15.30 (15.37)
10.05 (10.14)
13.70 (13.58)
8.86 (8.97)
13.62 (13.70)
13.48 (13.52)
10.87 (11.96)
8.94 (8.90)
10.25 (10.35)
10.27 (10.24)
9.24 (9.32)
11.10 (11.21)
13.07 (13.20)
8.80 (8.82)
11.27 (11.33)
11.16 (11.21)
10.15 (10.01)
9.86 (9.92)
9.04 (9.05)
9.31 (9.34)
9.22 (9.26)
8.42 (8.50)
10.08 (10.04)
10.12 (10.14)
9.96 (10.04)
9.77 (9.82)
9.70 (9.73)
8.83 (8.89)
10.65 (10.71)
10.57 (10.60)
8.46 (8.44)
6.94 (7.02)
6.95 (6.97)
12.58 (12.63)
9.55 (9.58)
9.83 (9.84)
9.07 (9.13)
7.65 (7.68)
7.55 (7.51)
6.10 (6.16)
7.46 (7.51)
7.17 (7.23)
5.93 (5.97)
7.25 (7.23)
5.92 (5.97)
7.03 (7.11)
7.00 (6.97)
5.72 (5.79)
5.76 (5.80)
4.91 (4.97)
11.56 (11.57)
11.38 (11.44)
10.36 (10.30)
7.95 (7.97)
10.66 (10.03)
9.61 (9.65)
7.52 (7.56)
9.34 (9.40)
8.50 (8.56)
8.12 (8.17)
7.15 (7.28)
7.23 (7.01)
162–165/0.02
165–175/0.02
100–103/0.05
Oil
8.05 (8.18)
21.15 (21.13)
16.60 (16.75)
15.33 (15.37)
18.04 (18.17)
13.68 (13.76)
9.10 (9.08)
22.17 (22.21)
17.52 (17.60)
16.06 (16.08)
14.47 (14.52)
9.47 (9.58)
15.23 (15.26)
15.60 (15.87)
12.56 (12.61)
17.11(17.13)
30.26 (30.32)
26.61 (26.70)
28.85 (28.89)
31.20 (31.24)
20.27 (20.37)
16.66 (16.72)
20.33 (20.37)
19.60 (19.61)
16.14 (16.21)
19.45 (19.61)
16.33 (16.21)
28.90 (28.94)
18.92 (18.90)
15.67(15.72)
18.35 (18.37)
15.70 (15.72)
15.65 (15.70)
10.33 (10.35)
9.50 (9.32)
8b
8c
8d
8e
64–66 (pentane)
98–100 (hexane)
101–102 (cyclohexane)
65–67 (heptane)
Oil
C
18H29N4PS
C14H21N4PS
12H24N3O2PS
C11H21N2O2PS2
14H30N5OP
C
8f
10a
10b
10c
10e
10f
11
12a
12b
13
Oil
C
47–49 (pentane)
79–81 (hexane)
Oil
122–124/0.02
112–114 (Et2O)
91–92 (EtOAc)
119–120 (EtOAc)
36–38 (Et2O)
62–64 (hexane)
170/0.05
95–96 (Et2O)
168–170 (Et2O)
94–95 (Et2O)
210–212 (Et2O)
Oil
192–193 (Et2O)
218–219 (Et2O)
Oil
135–140 (CHCl3)
231–232 (CH3CN)
194–195 (Et2O)
272–273 (Et2O)
207–208 (Et2O)
233–234 (Et2O)
140–145/0.05
143–146/0.05
205–210/0.05
140–141 (Et2O)
Oil
C13H27N4OPS
C18H29N4OP
C
12H24N3O3P
C11H21N2O3PS
C10H16Cl2F3N4OP
C15H33IN5P
C14H30IN4PS
C10 20
C14H26N7P
12H20ClN6P
H N3O2P
14
15
16
C
C14 26
C18 30
C15 21
C30 27
H
H
H
H
N7OP
N9P
N6PS3
N6P
17a
17b
17c
18b
19b
19c
20b
20c
21a
21b
21c
22b
22c
23a
23b
23c
25
26
27
28
29
30
31
32a
32b
C
15H21N6PS3
C15 21
C30 27
H
N6OPS3
N6OP
H
C
15H21N6OPS3
C30 27
C18 30
C15 21
C30 27
C22 28
C37 34
H
H
N6OP
N9PS
H
H
N6PS4
N6PS
H
H
N7OPS3
N7OP
C
12H15ClN3P
C11H12ClN2PS
C16H14ClN2P
C18H25N6PS
C7H10Cl4N3P
C8H10Cl4N3P
C14H20Cl3N6P
C10H16Cl3N4P
21.64 (21.63)
13.54 (13.60)
13.06 (13.09)
20.48 (20.51)
16.97 (17.00)
15.47 (15.49)
22.10 (22.18)
19.71 (19.74)
19.05 (19.02)
130/0.05
210/0.05
140–150/0.05
122–123 (pentane)
118–119 (pentane)
Oil
C
C
10H16Cl3N4PS
14H28ClN6PS
C14H20Cl3N6OP
C14H20Cl3N6PS
Oil
(Continued)
Heteroatom Chemistry DOI 10.1002/hc

292 Yurchenko et al.
TABLE 2 Continued
Found (Calcd) (%)
Mp (◦C) (Cryst. solvent)
Bp/pressure, (◦C)/Torr
Molecular
Formula
Compound
Yield (%)
N
P
32c
33a
33b
34a
35a
35b
35c
36a
36b
36c
37a
37b
78
97
86
81
77
79
35
75
74
80
65
50
Oil
Oil
C20H25Cl3N7P
19.60 (19.58)
25.28 (25.30)
24.36 (24.41)
9.22 (9.31)
12.80 (12.92)
8.75 (8.53)
7.55 (7.82)
12.20 (12.31)
8.25 (8.13)
6.15 (6.18)
6.94 (6.99)
6.68 (6.75)
6.83 (6.86)
9.43 (9.52)
9.45 (9.43)
8.57 (8.64)
9.02 (9.07)
9.02 (8.99)
8.25 (8.27)
7.10 (7.20)
7.08 (7.14)
C
18H32ClN8OP
H
174–175 (Et2O)
161–164
C18 32ClN8PS
C19H23IN3P
C18H20N3OP
C17H17N2OPS
C22H19N2OP
C18H20N3PS
109–110 (hexane)
145–146 (cyclohexane)
120–121 (pentane)
78–80 (hexane)
137–135 (MeOH)
184–185 (Et2O)
145–147 (hexane)
93–94 (pentane)
C
17H17N2PS2
H
C22 19N2PS
7.62 (7.48)
12.92 (13.01)
9.67 (9.69)
C25H27N4OP
C24H24N3OPS
thus providing synthetic routes to diverse types of
phosphorus(III) compounds such as 3a–d, 4, 6a,b,
and 7c (Scheme 1). Phosphonamidous chloride 4
reacts with the trifluoromethyl(dichloro)methanide
ion CF3CCl−2 [17] to produce functional phosphinous
amide 5.
Compounds 3a–d, 5, and 6a,b can be converted
to a diversity of phosphorus(V) derivatives 8–10 and
11 by classical methods (Scheme 2). The alkylation
of diamides 3a–c with CH3I affords phosphonium
salts 12a–c in about 30% yield. Phosphonate 6a re-
acts with CH3I producing phosphinate 13 by the
Arbuzov-type rearrangement. The reaction was con-
ducted without heating (at 20◦C) to minimize the
competing alkylation at the imine nitrogen atom in
the imidazole ring (Scheme 2).
The structure of diamide 8b was determined by
X-ray diffraction analysis. According to their data
(Fig. 1), the phosphorus atom is located near the het-
erocyclic C-5 atom thus pointing to the regioselective
5-phosphorylation of imidazole 1b. 13C NMR chem-
ical shifts are rather close for 8b (126.6 ppm) and
8a,c,d (122–125 ppm) as well as for 2b (128.7 ppm)
and 2a,c,d (127–129 ppm), which suggests that imi-
dazoles 1a,c are also phosphorylated at position 5.
We attempted the preparation of bis(imidazol-
5-yl)phosphinous chloride analogous to 15 by phos-
phorylation of imidazoles 1a–c with PCl3 in a 4:1
ratio, but the desired products could not be iso-
lated as individual compounds from the result-
ing mixture of mono-, di-, and trihalosubstituted
derivatives. However, the compound of this type,
N
N
N
Cl
I
C2Cl6
MeI
+
+
R"R'P
R
(Et2N)2P
R
R'R''P
R
N
N
N
3a–c
Me
Me
Cl
Me
Me
3a–d, 6a,b, 5
9a–c
12a,b
H2O2
MeI
S8
N
Na2CO3
6a,b, 5
N
N
R
O
P
i-PrO
Me
NMe2
R'R''P
R
R'R''P
O
N
N
N
S
Me
Me
Me
8a–f
13
10a–c,e,f, 11
3, 8–10: R' = R'' = Et2N (a–c), Me2N (d), i-PrO (e, f); R=NMe2 (a, e), SMe (b, f), Ph (c, d)
6: R' = R'' = i-PrO; R = NMe2 (a), SMe (b)
5, 11: R' = Me2N, R" = CF3CCl2; R = NMe2
12: R = NMe2 (a), SMe (b)
SCHEME 2
Heteroatom Chemistry DOI 10.1002/hc

5-Phosphorylated 1,2-Disubstituted Imidazoles 293
Remarkably, imidazole 1a remains unreactive to-
ward Me2NPCl2 at 20◦C, whereas rise of temperature
results in the 31P NMR-detected mixture of 2a and
17a obviously generated in the reaction between 1a
and PCl3 formed during Me2NPCl2 disproportiona-
tion. The structures of product 14 and its oxide 16
1
were confirmed by H and 13C NMR spectra. When
distilled, chloride 15 partially (up to a 10% degree)
disproportionates to phosphonous dichloride 2a and
tris(imidazol-5-yl)phosphine 17a.
Synthesis of Tris(imidazolyl)Phosphines
The most reactive imidazole 1a is phosphorylated
with PCl3 regioselectively in a 3:1 ratio in the pres-
ence of triethylamine to produce tris(imidazol-5-
yl)phosphine 17a (δP −85.4 ppm) in about 70% yield;
the reaction is completed at 25◦C within 30 h. For
the phosphorylation of imidazoles, 1b,c was applied
PBr3 in a 6:1 ratio (see Scheme 4) and reaction
proceeds regiospecifically to yield, in each case, a
mixture of two isomeric tertiary phosphines, 17 and
18. As evidenced by 31P NMR spectra (in pyridine),
FIGURE 1 Molecular structure of compound 8b.
chloride 15, was obtained by reaction of 5-
lithiated imidazole 1a with dimethylphosphorami-
dous dichloride, Me2NPCl2, followed by treatment
of phosphine amide 14 with PCl3 (Scheme 3).
N
N
N
O
H2O2
1. t-BuLi/THF
P
Me2NP
NMe2
NMe2
N
NMe2
2. Me2NPCl2
N
N
2
Me2N
2
Me
Me
1a
Me
14
16
PCl3
N
Cl
P
NMe2
N
2
Me
15
SCHEME 3
R
N
Me
N
N
N
N
N
N
1/6 PBr3;
Py
1/3 PCl3
+
P
3
R
P
R
N
Me2N
P
R
N
N
Py, Et3N
N
2
Me
18b, c
3
Me
17b, c
Me
Me
1a–c
17a
R
H2O2
R
N
Me
N
N
N
O
t-BuLi, PCl3
P
R
P
3
+
Ph
P
3
N
N
N
O
2
Me
20b, c
Me
19b, c
Me
17c
R = NMe2 (a), SMe (b), Ph (c).
SCHEME 4
Heteroatom Chemistry DOI 10.1002/hc

294 Yurchenko et al.
termined by X-ray diffraction analysis (Figs. 2 and
3), which also supported the structures of starting
phosphines 17c and 18c. Regarding phosphines 17b
and 18b as well as the corresponding phosphine ox-
ides 19b and 20b, their structures appear to be un-
doubtedly agree well with 31P, 1H, and 13C NMR spec-
tral data (Tables 2–4).
It has been found that phosphorylation of imi-
dazoles 1b,c is favored in the presence of 1 equiv of
LiBr. In this case, the reaction requires much milder
conditions: for 1b at 30◦C for 7 days against heating
at 70◦C for 4 days and for 1c 3 days against 7 days
at 75◦C, with the 17:18 isomer ratio remaining un-
changed. It should be noted that the lithiated deriva-
tive of imidazole 1c reacts regioselectively with PCl3
to give only phosphine 17c, which is spectrally iden-
tical to the tertiary phosphine obtained by direct
phosphorylation. Since lithiation of imidazole 1b
is impossible without the SMe group involving, the
metal-mediated synthesis cannot afford phosphines
17b and 18b, so that direct phosphorylation is the
only accessible to these compounds.
Comparing the NMR spectra of compounds
17b,c, and 18b,c, it is obvious that phosphoryla-
tion even of a single imidazolyl residue at position
4 causes a 2–3 ppm downfield shift of 31P NMR sig-
nals, which indicates less electron density on the 4-C
than on 5-C atom. The same trend holds for 13C res-
onances in these tertiary phosphines: The doublet
peak of the quaternary 4ꢁ-C atom (δC 132.9 ppm) is
shifted downfield from the analogous signal of the
quaternary 5-C atom (δC 123–124 and 129.7 ppm
for 17b,c and 18b,c, respectively). Thus, 31P and
13C NMR chemical shifts provide a reliable criterion
to distinguish between 4- and 5-phosphorylated 1,2-
disubstituted imidazoles.
FIGURE 2 Molecular structure of compound 19c.
there are two upfield signals, which correspond to
17b (δP −86.0 ppm) and 18b (δP −83.0 ppm) or to
17c (δP −85.0 ppm) and 18c (δP −82.0 ppm) and ex-
hibit an approximately 3:1 integral intensity ratio for
17 and 18. Isomers 17b and 18b were separated by
chromatography on silica gel. Compound 17c was
isolated by crystallization and oxidized to phosphine
oxide 19c then the remaining mixture enriched in
phosphine 18c was treated with hydrogen peroxide
followed by chromatographic isolation of the corre-
sponding phosphine oxide 20c (see Scheme 4). The
structure of phosphine oxides 19c and 20c was de-
Starting from tris(imidazol-5-yl)phosphines 17,
phosphorus(V) derivatives 21 and 22 were also pre-
pared (see Scheme 5).
Reactions of 1,2-Disubstituted Imidazoles 1a–c
with RPCl2
Imidazoles 1a–c are phosphorylated with PhPCl2 to
yield phosphine chlorides 23a–c (Scheme 6). The
ease of the reaction is less than with PHal3 and
strongly dependent on the electronic nature of the
2-substituent. With a two-fold excess of PhPCl2, en-
sured only monosubstitution to occur, phosphoryla-
tion is completed within 4 h for imidazole 1a (20◦C),
48 h for 1b (65◦C), and 72 h for 1c (130◦C). Just as
in the reaction with PHal3, under such conditions
imidazole 1c is phosphorylated with an equimolar
amount of PhPCl2 and pyridine in place of starting
imidazole acts as a hydrogen chloride acceptor.
FIGURE 3 Molecular structure of compound 20c.
Heteroatom Chemistry DOI 10.1002/hc

5-Phosphorylated 1,2-Disubstituted Imidazoles 295
TABLE 3 Spectroscopic Data of 5-Phosphorylated-1,2-Disubstituted Imidazoles
1H NMR, δ (ppm), J (Hz)
31P NMR
Compound Solvent
δ (ppm)
N-CH3
4-H
Other Signals
2a
2b
2c
C6D6
C6D6
C6D6
126.90
120.50
128.70
3.30 (s, 3H) 7.22 (s, 1H)
3.32 (s, 3H) 7.35 (s, 1H)
3.41 (s, 3H) 7.52 (s, 1H)
2.35 (s, 6H, NCH3)
2.34 (s, 3H, SCH3)
7.39 (t, 2H, 3.5, 2,6-H-Ph); 7.08–7.09 (m, 3H, 3,5-
and 4-H-Ph)
2d
3a
3b
3c
C6D6
C6D6
C6D6
C6D6
104.30
75.2
3.41 (s, 3H) 7.47 (s, 1H)
7.35 (m, 2H, 2,6-H-Ph); 7.05–7.07 (m, 3H, 3,5- and
4-H-Ph)
3.23 (s, 3H) 7.25 (d, 1H, 2.5) 2.62 (s, 6H, NCH3); 0.94 (t, 12H, 7.2, PNCH2CH3);
3.03 (m, 8H, PNCH2)
3.25 (s, 3H) 7.40 (d, 1H, 2.5) 2.45 (s, 3H, SCH3); 0.89 (t, 12H, 7.2, PNCH2CH3);
2.95 (m, 8H, PNCH2)
3.30 (s, 3H) 7.50 (d, 1H, 2.5) 7.68 (d, 2H, 7.5, 2,6-H-Ph) 2.99 (m, 8H, PNCH2);
7.16 (t, 1H, 7.5, 4-H-Ph); 7.09 (m, 2H, 3,5-H-Ph);
74.7
75.1
0.91 (t, 12H, 7.0, NCH2CH3)
3.20 (s, 3H) 7.41 (d, 1H, 2.5) 2.55 (d, 12H, 9.5, PNCH3); 7.10 (m, 2H, 3,5-H-Ph);
7.17 (t, 1H, 7.5, 4-H-Ph); 7.63 (d, 2H, 7.5, 2,6-H-Ph)
3d
C6D6
81.9
4
5
6a
C6D6
C6D6
C6D6
120.90
51.50
144.7
3.05 (s, 3H) 7.55 (s, 1H)
3.35 (s, 3H) 7.90 (s, 1H)
3.40 (s, 3H) 7.53 (s, 1H)
2.36 (d, 6H, 13.5, P-NCH3); 2.53 (s, 6H, NCH3)
2.50 (s, 6H, NCH3); 2.50 (d, 6H, 9.30, P-NCH3)
2.52 (s, 6H, NCH3); 1.10 (dd, 12H, 9.0, POCHCH3);
4.20 (m, 2H, POCH)
6b
C6D6
145.2
3.38 (s, 3H) 7.62 (s, 1H)
2.40 (s, 3H, SCH3); 1.05 (dd, 9H, 21.0, POCHCH3);
4.12 (m, 2H, POCH)
7a
7b
7c
CDCl3
CDCl3
CDCl3
−33.2
−33.5
−33.0
3.40 (s, 3H) 6.50 (s, 1H)
3.45 (s, 3H) 6.71 (s, 1H)
3.66 (s, 3H) 6.75 (s, 1H)
2.80 (s, 6H, NCH3); 7.33 (br s, 10H, H-Ph)
2.62 (s, 3H, SCH3); 7.34 (d, 3.9, 10H, H-Ph)
7.38 (br s, 10H, H-Ph-P); 7.62 (d, 1.2, 2,6-H-Ph);
7.40–7.50 (m, 3,5- and 4-H-Ph)
8a
8b
8c
CDCl3
CDCl3
CDCl3
59.8
63.3
58.9
3.68 (s, 3H) 7.00 (s, 1H)
3.67 (s, 3H) 7.21 (s, 1H)
3.75 (s, 3H) 7.39 (s, 1H)
2.89 (s, 6H, NCH3); 1.09 (t, 12H, 7.0, PNCH2CH3);
3.19 (q, 8H, 12.50, PNCH2)
2.64 (s, 3H, SCH3); 1.10 (t, 12H, 7.0, PNCH2CH3);
3.20 (q, 8H, 12.50, PNCH2)
1.13 (t, 12H, 7.0, PNCH2CH3); 3.25 (q, 8H, 12.50,
PNCH2); 7.45–7.50 (m, 3H, 3,5- and 4-H-Ph); 7.6
(d, 2H, 7.5, 2,6-H-Ph)
8d
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
64.7
68.9
68.1
16.9
17.3
16.3
3.92 (s, 3H) 7.38 (s, 1H)
3.89 (s, 3H) 7.30 (s, 1H)
3.69 (s, 3H) 7.53 (s, 1H)
3.60 (s, 3H) 6.96 (s, 1H)
3.61 (s, 3H) 7.22 (s, 1H)
3.73 (s, 3H) 7.33 (s, 1H)
2.75 (d, 6H, 5.0, PNCH3); 7.1 (m, 2H, 3,5-H-Ph); 7.2
(t, 1H, 7.5, 4-H-Ph); 7.6 (d, 2H, 7.5, 2,6-H-Ph)
1.31 (dd, 12H, 6.0, 46.0, POCHCH3); 2,78 (s, 6H,
NCH3); 4.86 (q, 2H, 6.0, POCH)
1.31 (dd, 12H, 6.0, 50.10, POCHCH3); 2,66 (s, 3H,
SCH3); 4.87 (q, 2H, 6.0, POCH)
2.75 (s, 6H, NCH3); 1.09 (t, 12H, 7.0, PNCH2CH3);
3.19 (m, 8H, PNCH2)
2.64 (s, 3H, SCH3); 1.07 (t, 12H, 7.0, PNCH2CH3);
3.08 (m, 8H, PNCH2)
8e
8f
10a
10b
10c
7.60 (d, 2H, 6.5, 2,6-H-Ph); 7.41–7.50 (m, 3H, 6.5,
3,5- and 4-H-Ph); 1.11 (t, 12H, 7.0, PNCH2CH3);
3.15 (m, 8H, PNCH2)
10e
10f
CDCl3
CDCl3
6.9
6.4
3.89 (s, 3H) 7.32 (s, 1H)
3.58 (s, 3H) 7.44 (s, 1H)
3.65 (s, 3H) 7.63 (s, 1H)
2.78 (s, 6H, NCH3); 1.30; (dd, 12H, 40.5, POCHCH3);
4.67 (q, 2H, 2.50, POCH)
2.57 (s, 3H, SCH3); 1.24 (dd, 12H, 45.0, POCHCH3);
4.62 (q, 2H, 2.50, POCH)
11
12a
CDCl3
CD3CN
20.00
44.00
2.85 (s, 6H, NCH3); 2.87 (d, 6H, 9.30, P-NCH3)
3.50 (s, 3H) 7.39 (d, 1.5, 1H) 1.18 (t, 12H, 7.2, PNCH2CH3); 2.22 (d, 3H, 13.50,
P+-CH3); 2.86 (s, 6H, NCH3); 3.18 (q, 8H, 10.50,
PNCH2)
12b
CD3CN
43.40
3.56 (s, 3H) 7.61 (d, 1.2, 1H) 1.84 (t, 12H, 7.2, PNCH2CH3); 2.24 (d, 3H, 13.50,
P+-CH3); 2.69 (s, 3H, SCH3); 3.18 (m, 8H, PNCH2)
(Continued)
Heteroatom Chemistry DOI 10.1002/hc

296 Yurchenko et al.
TABLE 3 Continued
1H NMR, δ (ppm), J (Hz)
31P NMR
Compound Solvent
δ (ppm)
N-CH3
4-H
Other Signals
13
CDCl3
31.1
3.68 (s, 3H) 7.22 (s, 1H)
2.82 (s, 6H, NCH3); 1.33 (dd, 12H, 6.3, POCHCH3);
1.68 (d, 3H, 15.0, CH3); 4.67 (m, 2H, POCH)
2.45 (d, 6H, 10.0, PNCH3); 2.55 (s, 12H, NCH3)
2.47 (s, 12H, NCH3)
14
15
16
17a
17b
17c
C6D6
C6D6
CDCl3
CDCl3
CDCl3
CDCl3
13.40
31.50
10.70
- 84.0
- 85.8
- 84.8
3.04 (s, 6H) 7.20 (s, 2H)
3.29 (s, 6H) 7.24 (s, 2H)
3.25 (s, 6H) 6.76 (d, 2H, 1.50) 2.61 (d, 6H, 10.0, PNCH3); 2.67 (s, 12H, NCH3)
3.50 (s, 9H) 6.56 (s, 3H)
3.32 (s, 9H) 6.93 (s, 3H)
2.66 (s, 18H, NCH3)
2.84 (s, 9H, SCH3)
7.39 (d, 3H, 4-H-Ph); 7.44 (t, 6H, 2,6-H-Ph); 7.61 (d,
6H, 3,5-H-Ph)
3.50 (s, 9H
7.10 (s, 3H)
18b
CDCl3
−83.4
3.56 (s, 6H) 6.15 (s, 2H)
2.60 (s, 6H, SCH3); 2.62 (s, 3H, SCH3); 3.53 (s, 3H,
NCH3); 7.03 (s, 1H, 5-H)
19b
19c
CDCl3
CDCl3
−8.2
−4.8
3.57 (s, 9H) 6.94 (s, 3H)
3.73 (s, 9H) 7.15 (s, 3H)
2.70 (s, 9H, SCH3)
7.50 (m, 9H, 2,6+4-H-Ph); 7.66 (d, 6H, 3,5-H-Ph,
7.00)
20b
20c
CDCl3
CDCl3
−3.9
−2.8
4.00 (s, 6H) 7.28 (s, 2H)
3.73 (s, 6H) 7.40 (s, 2H)
3.88 (s, 9H) 6.59 (s, 3H)
3.74 (s, 9H) 6.90 (d, 1.80, 3H) 2.68 (s, 9H, SCH3)
4.02 (s, 9H) 7.10 (s, 3H)
3.55 (s, 9H) 7.09 (s, 3H)
2.69 (s, 6H, SCH3); 2.61 (s, 3H, SCH3); 3.61 (s, 3H,
NCH3); 7.52 (s, 1H, 5-H)
7.36 (m, 9H, 2,6+4-H-Ph); 7.55 (d, 6H, 3,5-H-Ph,
7.00); 7.66 (s, 1H, 5-H)
21a
21b
21c
22b
CDCl3
CDCl3
CDCl3
CDCl3
−6.6
−9.2
−5.0
−40.4
2.72 (s, 18H, NCH3)
7.50 (br s, 9H, o- and p-H-Ph); 7.66 (br s, 6H, m-Ph)
2.65 (s, 9H, SCH3); 3.72 (s, 3H, OCH3); 6.60 (q, 4H,
15.60, 2,6 and 3,5-H-Ar)
22c
CDCl3
−37.8
3.87 (s, 9H) 7.33 (s, 3H)
3.72 (s, 3H, OCH3); 6.70 (s, 4H, 2,6- and 3,5-H-Ar);
7.50 (d, 9H, 7.50, 2,6- and 4-H-Ph); 7.66 (d, 6H,
7.50, 3,5-H-Ph)
23a
23b
23c
25
C6D6
C6D6
C6D6
CDCl3
54.80
53.00
54.55
9.70
3.34 (s, 3H) 7.02 (s,1H)
3.00 (s, 3H) 7.31 (s, 1H)
3.18 (s, 3H) 7.45 (s, 1H)
3.63 (s, 6H) 6.61 (s, 2H)
2.82 (s, 6H, NCH3); 7.41 (br s, 3H, 2,6-H-Ph,
4-H-Ph); 7.60 (d, 2H, 7.5, 3,5-H-Ph)
2.37 (s, 3H, SCH3); 7.02 (br s, 3H, 2,6- and 4-H-Ph);
7.46 (d, 2H, 7.5, 3,5-H-Ph)
7.10 (m, 6H, 3,4,5-Ph and 3,4,5-PhP); 7.47 (m, 2H,
2,6-H-PhP); 7.61 (m, 2H, 2,6-H-Ph)
2.83 (s, 12H, NCH3); 7.54 (m, 2H, 3,5-Ph); 7.59 (m,
1H, 4-Ph); 7.87 (dd, 2H, 7.0; 15.0, 2,6-Ph)
2.87 (s, 6H, NCH3)
2.43 (s, 6H, NCH3)
2.51 (s, 12H, NCH3)
2.57 (d, 6H, 9.50, PNCH3); 2.62 (s, 6H, NCH3)
2.77 (br s, 12H, NCH3)
2.66 (d, 6H, 12.00, P-NCH3); 2.74 (s, 12H,
C CNCH3); 2.78 (s, 6H, NCH3)
26
27
28
29
30
31
C6D6
C6D6
C6D6
C6D6
CDCl3
CDCl3
75.50
49.70
−50.20
39.30
48.00
49.20
3.70 (s, 3H) 7.82 (s, 1H)
3.48 (s, 3H) 7.45 (s, 1H)
3.12 (s, 6H) 7.29 (s, 2H)
3.15 (s, 3H) 7.23 (s, 1H)
3.45 (s, 6H) 7.00 (s, 2H)
3.65 (s, 3H) 7.17 (s, 1H)
32a
32b
32c
CDCl3
CDCl3
CDCl3
4.70
13.00
−29.70
3.61 (s, 6H) 6.90 (d, 1.50, 2H) 2.79 (s, 12H, NCH3)
3.23 (s, 6H) 6.90 (d, 2H, 1.80) 2.86 (s, 12H, NCH3)
3.70 (s, 6H) 7.62 (s, 2H)
2.48 (s, 12H, NCH3); 6.71 (t, 1H, 7.5, 4-H-Ph); 6.90
(d, 2H, 7.5, 2,6-H-Ph); 7.10 (d, 2H, 7.5, 3,5-H-Ph);
2.58 (s, 12H, NMe2); 2.62 (d, 12H, 15.00,
C CNCH3)
33a
CDCl3
6.10
3.30 (s, 6H) 6.66 (s, 2H)
33b
34a
CDCl3
CD3CN
11.30
7.89
3.39 (s, 6H) 6.70 (s, 2H)
3.35 (s, 3H) 7.12 (s, 1H)
2.47 (d, 12H, 3.50, C CNCH3); 2.50 (s, 12H, NCH3)
2.88 (s, 6H, NCH3); 2.83 (br d, 3H, 12.50, PCH3);
7.76 (br s, 8H, 2,6- and 3,5-H-Ph); 7.9 (s, 2H,
4-H-Ph)
35a
CDCl3
17.7
3.50 (s, 3H) 6.58, (s 1H)
2.80 (s, 3H, NCH3); 7.47–7.53 (m, 4H, 3,5-H-Ph);
7.56 (d, 2H, 7.00, 4-H-Ph); 7.70 (q, 4H, 12.50,
2,6-H-Ph)
35b
35c
CDCl3
CDCl3
17.1
17.9
3.60 (s, 3H) 6.82 (s, 1H)
3.73 (s, 3H) 6.90 (s, 1H)
2.70 (s, 3H, SCH3); 7.51 (m, 4H, 3,5-H-Ph); 7.60 (t,
4H, 7.50, 4-H-Ph); 7.71 (q, 4H, 13.00, 2,6-H-Ph)
7.50 (m, 12H, Ph and 3,5-H-PhP); 7.60 (d, 2H, 7.50,
4-H-PhP); 7.75 (q, 4H, 12.50, 2,6-H-PhP)
(Continued)
Heteroatom Chemistry DOI 10.1002/hc

5-Phosphorylated 1,2-Disubstituted Imidazoles 297
TABLE 3 Continued
1H NMR, δ (ppm), J (Hz)
31P NMR
Compound Solvent
δ (ppm)
N-CH3
4-H
Other Signals
36a
36b
36c
37a
CDCl3
CDCl3
CDCl3
CDCl3
26.7
26.1
3.73 (s, 3H) 6.40 (s, 1H)
3.50 (s, 3H) 6.65 (s, 1H)
3.60 (s, 3H) 6.75 (s, 1H)
3.35 (s, 3H) 6.80 (s, 1H)
2.80 (s, 3H, NCH3); 7.43–7.56 (m, 6H, 3,5- and
4-H-Ph); 7.80 (q, 4H, 13.80, 2,6-H-Ph)
2.70 (s, 3H, SCH3); 7.50 (m, 4H, 3,5-H-PhP); 7.58 (t,
8.0, 4-H-Ph); 7.80 (q, 4H, 13.00, 2,6-H-Ph)
7.45 (br s, 12H, Ph+3,5-H-PhP); 7.55 (dd, 2H,
4-H-PhP); 7.80 (q, 4H, 13.50, 2,6-H-PhP)
2.78 (s, 3H, NCH3); 3.71 (s, 3H, OCH3); 6.64 (d, 2H,
8.5, 3,5-H-Ar); 6.75 (d, 2H, 8.5, 2,6-H-Ar); 7.45 (m,
4H, 3,5-H-Ph); 7.52 (t, 2H, 7.5, 4-H-Ph); 7.78 (q,
4H, 12.50, 2,6-H-Ph)
27.3
−16.0
37b
CDCl3
−10.6
3.28 (s, 3H) 7.03 (s, 1H)
2.63 (s, 3H, SCH3); 3.37 (s, 3H, OCH3); 6.64 (d, 2H,
8.5, 3,5-H-Ar); 6.75 (d, 2H, 8.5, 2,6-H-Ar); 7.42 (m,
4H, 3,5-H-Ph); 7.50 (t, 2H, 7.5, 4-H-Ph); 7.78 (q,
4H, 12.50, 2,6-H-Ph)
38a
38b
38c
CD3CN
DMSO
CD3CN
14.60
55.20
61.40
3.66 (s, 3H) 7.31 (s, 1 H)
3.94 (s, 3H) 8.10 (s, 1H)
3.68 (s, 3H) 7.90 (s, 1H)
1.10 (t, 12H, 12.00, PNCH2CH3); 3.05 (s, 6H, NCH3);
3.10 (m, 8H, PNCH2); 3.74 (s, 3H, N+-CH3)
1.01 (t, 12H, 6.70, PNCH2CH3); 2.58 (s, 3H, SCH3);
3.18 (m, 8H, 6.70, PNCH2); 4.00 (s, 3H, N+-CH3)
2.80 (d, 12H, 12.50, PNCH3); 3.78 (s, 3H, N+-CH3);
7.68 (d, 2H, 7.50, 2.6-H-Ph); 7.73 (t, 1H, 7.50,
4-H-Ph); 7.80 (t, 2H, 7.50, 3,5-H-Ph)
38d
38e
38f
CDCl3
CDCl3
CDCl3
17.10
28.20
16.50
3.60 (s, 3H) 6.63 (d, 2.5, 1H) 3.22 (s, 3H, NCH3); 3.81 (s, 3H, N+-CH3); 7.62 (m,
6H, 3,5- and 4-H-Ph); 8.05 (dd, 13.20, 6.60, 4H,
2,6-H-Ph)
3.90 (s, 3H) 6.90 (d, 2.1, 1H) 2.80 (s, 3H, SCH3); 4.04 (s, 3H, N+-CH3); 7.63 (m,
6H, 3,5- and 4-H-Ph); 8.25 (dd, 14.70, 7.80, 4H,
2,6-H-Ph)
3.64 (s, 3H) 7.13 (d, 2.1, 1H) 3.85 (s, 3H, N+-CH3); 7.66 (m, 9H,
3,5-H-PhP+H-Ph); 7.92 (d, 2H, 6.60, 4-H-PhP);
8.18 (dd, 13.20, 8.00, 4H, 2,6-H-PhP)
Chlorides 23a–c appear as air-sensitive yellow
liquids distillable in vacuo and represent quite re-
active compounds. For instance, compound 23a re-
acts with 1a in a 1:2 ratio to afford bis(imidazol-5-
yl)phenylphosphine 24a, which exhibits a 31P NMR
chemical shift (δP −81 ppm) being characteristic of
tertiary phosphines. Compound 24a was transferred
to phosphine sulfide 25a, with its structure con-
firmed by 1H and 13C NMR and mass spectral data.
We studied the chemical behavior of the most re-
active imidazole 1a toward other phosphine dichlo-
rides RPCl2 containing electron-withdrawing groups
(R CCl3; CCl2 CCl–). Compound 1a reacts with
trichloromethylphosphine dichloride in pyridine at
60◦C, but the reaction results in a low yield of prod-
uct 26 (26%) and is accompanied by tar formation
(Scheme 7). Phosphine chloride 26 is thermally un-
stable and partially decomposes on vacuo distilla-
tion to form phosphine dichloride 2a. Nevertheless,
by treatment of the latter 2a with trichloromethane
ion CCl−3 [18] chloride 26 is formed in a moderate
yield (61%) and does not need to be purified by dis-
tillation.
Imidazole 1a readily reacts with trichlorovinyl-
phosphine dichloride CCl2 CClPCl2 [19] in a 2:1
or 4:1 ratio producing monohalo- (27) or dihalo-
substituted product (28), respectively (Scheme 8).
Phosphine chloride 27 enters into the reaction
with dimethyl(trimethylsilyl)amine to give amide
29. It is notable that phosphine sulfide 30 reacts
with dimethylamine so that the β-chlorine atoms
in the trichloroethenyl residue are substituted by
dimethylamino groups and tetramethylethylendi-
amino derivative 31 is formed. Tertiary phosphine
28 is easily oxidized with hydrogen peroxide, adds
sulfur, and undergoes the Staudinger reaction with
phenylazide, thus affording phosphorus(V) com-
pounds 32a–c. Like compound 30, they are con-
verted to ethylendiamino derivatives 33a,b by the
reaction with dimethylamine.
Synthesis of Diphenyl(imidazolyl)Phosphines
Diphenylphosphine halides Ph2PHal (Hal Cl, Br)
are the less reactive phosphorylating agents
among those involved in the present study and,
Heteroatom Chemistry DOI 10.1002/hc

298 Yurchenko et al.
TABLE 4 Spectroscopic Data of 5-Phosphorylated-1,2-Disubstituted Imidazoles: 13C NMR δ (Multiplicity in ppm) and JPC (Hz)
13C NMR
No
2a
2b
2c
2d
3a
3b
3c
Solvent
C6D6
C6D6
C6D6
C6D6
C6D6
C6D6
C6D6
N-CH3
32.07, s
31.86, s
C-2
C-4
C-5
Other Signals
161.12, d, 140.50, d, 128.85, d, 42.36, s
2.50 52.82 76.71
155.08, d, 141.50, d, 128.70, d, 14.38, s
2.00 57.85 78.0
157.34, d, 141.40, d, 127.08, d, 129.11 (d, 27.7, i-Ph); 130.20 (s, 2,6-Ph); 130.52 (s,
3.77
156.1, d,
3.77
34.36, d,
3.77
33.72, d,
2.52
30.80, d,
7.54
31.15, d,
6.30
50.3
141.01, d, 128.85, d, 129.35 (d, 11.3, i-Ph); 129.61 (s, 2,6-Ph); 129.90 (s,
52.82 46.53 4-Ph); 128.7(s, 3,5-Ph).
8.8
4-Ph); 129.33 (s, 3,5-Ph).
156.45, d, 131.54, d, 127.66, d, 42.65 (s, NCH3); 14.5 (d, 3.77, PNCH2CH3); 42.74 (d,
6.3
5.03
135.0, d,
5.03
24.00
132.3, d,
1.26
17.6, PNCH2)
146.0, d,
6.3
151.8, d,
6.29
14.36 (d, 3.77, PNCH2CH3); 42.74 (d, 16.35, PNCH2)
33.94, d,
8.80
135.94, d, 133.44, d, 132.75(s, i-Ph); 130.0 (s, 2,6-Ph); 129.0 (s, 4-Ph);
5.03
1.26
129.22 (s, 3,5-Ph); 15.43 (d, 3.8, PNCH2CH3); 43.9
(d, 17.6, PNCH2)
3d
4
C6D6
C6D6
C6D6
C6D6
C6D6
CDCl3
33.60, d,
7.54
30.78, s
151.9, d,
5.03
132.35, d, 136.24, d, 132.37 (s, i-Ph-P);130.0 (s, 2,6-Ph-P); 129.0 (s,
5.03 6.30 4-Ph-P); 29.22 (s, 3,5-Ph-P); 41.77 (d, PNCH3)
157.70, d, 134.57, d, 125.30, d, 39.10 (d, 11.30, PNCH3); 42.55 (s, NCH3)
5.03
156.90, d, 135.43, s
8.80
6.30
20.10
5
30.70, s
119.78, d, 41.10 (d, 19.00, PNCH3); 42.53 (s, NCH3); 84.80 (m,
13.80
CF3); 123.90 (dd, 16.35; 287.0, PCCl2CF3)
6a
6b
7a
31.06, d,
5.03
31.63, d,
5.03
157.02, d, 135.45, d, 129.70, d, 42.47 (s, NCH3); 3.48 (d, 3.77); 23.90 (d, 5.03,
5.03 2.64 21.38 POCH(CH3)2); 70.19 (d, 15.09, POCH)
147.76, d, 136.28, d, 134.10, d, 15.10 (s, SCH3); 24.15 (d, 3.77); 24.45 (d, 6.3,
2.51 22.64 26.41 POCH(CH3)2); 70.58 (d, 13.83, POCH)
123.90, d, 31.20 (s, NCH3); 133.20 (d, 20.12, i-Ph-P); 134.40 (d,
42.74, s
157.17, d, 128.9, s
5.00
5.00
6.3, 2,6-Ph-P); 135.33 (d, 6.3, 4-Ph-P); 128.53 (d,
7.54, 3,5-Ph-P)
7b
7c
CDCl3
CDCl3
31.83, d,
6.3
33.32, d,
12.6
147.60, d, 137.81, d, 134.80, d, 15.77 (s, SCH3); 128.90 (d, 7.6, i-Ph); 133.22 (d, 20.12,
8.80
151.85, d, 137.30, d, 128.57, s
2.50 2.50
5.03
6.30
2,6-Ph); 129.15 (s, 4-Ph); 128.68 (d, 18.86, 3,5-Ph)
128.88 (s, 4-Ph); 128.92 (s, 3,5-Ph-P); 128.72 (s,
3,5-Ph); 128.78 (s, 2,6-Ph); 129.24 (s, 4-Ph-P);
130.73 (s, i-Ph); 133.37; 133.53 (s, 2,6-Ph-P);
134.96 (d, 6.30, i-Ph-P)
8a
8b
8c
CDCl3
CDCl3
CDCl3
32.34, s
38.50, s
158.05, d, 134.07, d, 121.90, d, 13.80 (d, 2.5, PNCH2CH3); 39.76 (d, 5.03, PNCH2);
13.8
150.0, d,
11.0
50.3
162,2
42.50 (s, NCH3)
136.95, d, 126.62, d, 13.8(d, 3.0, PNCH2CH3); 15.23 (s, SCH3); 39.8 (d, 5.0,
15.1
157.2
PNCH2)
34.20, d,
2.50
153.00, d, 137.00, d, 125.2, d,
12.6 15.0 155.9
13.8 (s, PNCH2CH3); 39.9 (d, 3.77, PNCH2); 130.20
(d, 2.5, i-Ph); 129.11 (s, 2,6-Ph); 129.21 (s, 4-Ph);
128.52 (s, 3,5-Ph)
8d
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
34.10, s
30.04, s
32.41, s
31.86, s
32.30, s
33.88, s
153.03, d, 137.26, d, 123.91, d, 37.15 (d, 2.52, PNCH3); 128.28 (s, 3,5-Ph); 129.12 (s,
11.32 18.86 30.18 2,6-Ph); 129.32 (s, 4-Ph); 129.95 (s, i-Ph)
158.02, d, 137.43, d, 122.89, d, 24.36 (d, 3.77), 24.08 (d, 5.03, POCH(CH3)2); 42.51
15.09 20.12 152.17 (s, NCH3); 71.76 (d, 3.77, POCH)
150.13, d, 140.05, d, 127.48, d, 15.26 (s, SCH3); 23.46 (d, 5.03), 23.85 (d, 5.03,
8e
8f
13.83
157.606
d, 13.83
21.40
134.97, d, 120.87, d, 42.42 (s, NCH3); 14.07 (d, 1.26, PNCH2CH3); 38.86 (d,
16.35 190.0 6.30, PNCH2)
188.64
POCH(CH3)2); 71.96 (d, 5.03, POCH)
10a
10b
10c
149.21, d, 137.60, d, 125.60, d, 15.33 (s, SCH3); 14.09 (d, 1.26, PNCH2CH3); 39.86,
13.00 16.00 187.0 (s, PNCH2)
152.60, d, 137.77, d, 125.20, d, 14.14 (d, 2.51, PNCH2CH3); 39.06 (d, 5.03, PNCH2);
12.57
17.61
184.90
130.27(s, i-Ph); 129.07 (s, 2,6-Ph); 129.16 (s, 4-Ph);
128.53 (s, 3,5-Ph);
10e
CDCl3
31.90, s
157.90, d, 137.07, d, 117.7, d,
16.35 17.61 104.38
23.78, 24.08 (d, 5.03, d, 5.03, POCH(CH3)2); 42.51 (s,
NCH3); 71.18 (d, 5.03, POCH)
(Continued)
Heteroatom Chemistry DOI 10.1002/hc

5-Phosphorylated 1,2-Disubstituted Imidazoles 299
TABLE 4 Continued
13C NMR
No
10f
13
Solvent
CDCl3
CDCl3
N-CH3
32.01, s
32.07, s
C-2
C-4
C-5
Other Signals
149.71, d, 139.46, d, 122.50, d, 14.93 (s, SCH3); 23.51, 23.79 (d, 5.03, d, 5.03,
16.35
157.80. d, 135.73, d, 121.0, d,
13.83 15.09 155.94
18.86
227.62
POCH(CH3)2); 71.09 (d, 5.03, POCH)
17.53 (d, 109.41, P(O)CH3); 23.87 (d, 6.3), 24.53 (d,
2.51, POCH(CH3)2); 42.46 (s, NCH3); 69.80 (d, 6.30,
POCH)
12a CD3CN 33.83, s
12b CD3CN 33.90, s
161.84, d, 143.30, d, 111.50, d, 13.00 (d, 96.80, P+CH3); 14.04 (d, 2,50,
13.80
16.35
157.20
P+NCH2CH3); 41.08 (d, 5.03, P+NCH2); 42.40 (s,
NCH3)
155.68, d, 144.90, d, 116.55, d, 13.00 (d, 95.60, P+CH3); 14.00 (d, 2,50,
12.75
158.60, d, 139.40, d, 112.00, d, 37.37 (d, 3.80, PNCH3); 42.26 (s, NCH3); 80.00 (m,
16.35 15.09 174.80 CF3); 121.75 (qd, 5.03; 283.0, PCCl2CF3)
157.65, d, 134.40, d, 119.00, d, 42.50 (s, NCH3)
5.03 8.80 6.30
149.05, d, 138.10, d, 123.13, d, 15.57 (s, SCH3)
18.90
152.20
P+NCH2CH3); 15.44 (s, SCH3); (d, 3.80, P+NCH2)
11
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
32.50, s
17a
17b
17c
18b
19b
19c
20b
31.21, d,
8.80
31.84, d,
8.8
33.43, d,
12.57
32.02, d,
8.80
5.03
152.85, d, 138.0, d,
3.77 5.03
147.80, d, 138.15, d, 129.74, d, 33.00 (s, NCH3); 125.99 (d, 2.50, P-CC-5ꢁ); 132.94 (d,
3.80 13.80 40.24
17.60, P-C-4ꢁ); 146.44 (d, 12.75, C-2ꢁ)
152.40, d, 140.07, d, 124.04, d, 15.16 (s, SCH3)
11.32 18.86 144.62
154.80, d, 140.10, d, 124.02, d, 128.82 (s, 3,5-C-Ph); 129.20 (s, i-C-Ph); 129.26
11.32 17.61 144.62 (2,6-C-Ph); 129.90 (s, 4-C-Ph)
7.5
5.03
123.61, d, 130.25 (s, i-Ph); 128.90 (s, 2,6-Ph); 129.20 (s, 4-Ph);
7.54
128.66 (s, 3,5-Ph)
32.95, s
34.69, s
32.75, s
150.92, d, 140.14, d, 124.93, d, 15.27 (s, SCH3); 15.47 (s, SCHꢁ3); 33.28 (NCH3);
11.32
131.46 (d, 31.44, C-5ꢁ); 132.95 (d, 168.50, PC-4ꢁ);
17.61
139.60
147.65 (d, 22.64, C-2ꢁ)
20c
CDCl3
38.48, s
153.70, d, 140.12, d, 124.98, d, 35.13 (NCH3); 128.62 (s, 3,5-CPh); 128.68 (s,
11.32
16.35
137.08
3,5-CꢁPh); 128.87 (2,6-CꢁPh); 129.20 (2,6-CPh);
129.34 (s, i-CꢁPh); 129.49 (4-CPh); 129.51 (5-CꢁPh);
129.58 (i-CPh); 132.17 (d, 35.20, Cꢁ-5); 132.90 (d,
207.0, PCꢁ-4); 150.86 (d, 20.12, Cꢁ-2)
21a
21b
21c
22b
CDCl3
CDCl3
CDCl3
CDCl3
32.82, s
33.15, s
34.94, s
32.94, s
159.38, d, 136.90, d, 117.22, d, 42.47 (s, NCH3)
12.75 15.09 124.50
152.90, d, 139.50, d, 122.14, d, 15.13 (s, SCH3)
11.32 17.61 122.00
155.25 d, 139.43 d, 122.00, d, 128.81 (s, 3,5-C-Ph); 129.27 (s, i-C-Ph); 129.33
11.32
152.15, d, 140.35, d, 122.25,
10.06 13.83 br s
16.35
122.00
(2,6-C-Ph); 129.93 (s, 4-C-Ph)
15.10 (s, SCH3); 55.46 (s, OCH3); 114.57 (3,5-C-Ar);
123.20 (d, 16.35, 2,6-C-Ar); 141.92 (s, i-C-Ar);
152.94 (s, 4-C-Ar)
22c
23a
CDCl3
C6D6
34.78, s
31.86, s
154.60, d, 140.30, d, 123.10, d, 55.56 (s, OCH3); 114.71 (3,5-C-Ar); 123.30 (d, 17.60,
11.32
17.60
134.56
2,6-C-Ar); 128.78 (s, 3,5-C-Ph); 129.28 (s,
2,6-C-Ph); 129.32 (s, i-C-Ph); 129.84 (s, 4-C-Ph);
142.20 (s, i-C-Ar); 152.91 (s, 4-C-Ar)
158.97, d, 138.75, d, 124.36, d, 42.25 (s, NCH3); 128.60 (d, 6.2, 3,5-Ph); 129.88 (s,
2.50
35.21
49.00
4-Ph); 130.56 (d, 22.64, 2,6-Ph); 135.60 (d, 25.16,
i-Ph)
23b
23c
C6D6
C6D6
31.32, s
33.04, s
151.87, d, 142.00 d, 128.58 d, 14.75 (s, SCH3); 136.23 (d, 25.15, i-Ph); 128.67 (d, 6.3,
3.77 32.70 47.80 3,5-Ph); 129.85 (s, 4-Ph); 130.71 (d, 22.64, 2,6-Ph).
153.96, d, 140.95 d, 129.94 d, 128.41 (s, 3,5-Ph); 128.78 (d, 6.30, 3,5-PhP); 129.07
2.50
24.00
87.00
(s, 4-Ph); 129.20 (s, 2,6-Ph); 130.30 (s, 4-PhP);
130.36 (s, i-Ph); 131.27 (d, 24.00, 2,6-PhP); 135.66
(d, 24.00, i-PhP)
25a
CDCl3
32.85, s
159.30, d, 132.30, d, 118.56, d, 42.36 (s, NCH3); 128.60 (d, 12.75, 3,5-C-Ph); 130.20
12.75
10.10
108.80
(d, 95.60, i-C-Ph); 132.36 (s, 4-C-Ph); 136.62 (d,
13.83, 2,6-C-Ph)
(Continued)
Heteroatom Chemistry DOI 10.1002/hc

300 Yurchenko et al.
TABLE 4 Continued
13C NMR
No
14
Solvent
C6D6
N-CH3
C-2
C-4
C-5
Other Signals
30.60, s
156.92, d, 133.50, s
6.30
124.35, d, 40.24 (d, 16.35, PNCH3); 42.61 (s, NCH3)
2.50
15
C6D6
31.97, d,
6.30
32.10, s
159.53, d, 137.80, d, 121.73, d, 42.02 (s, NCH3)
5.03 28.00 33.00
158.25, d, 136.41, d, 119.78, d, 36.39 (s, P(O)NCH3); 42.28 (s, NCH3)
13.83 17.60 37.73
159.50, d, 139.22, d, 120.22, d, 41.94 (s, NCH3); 129.07 (d, 45.27,C CCl2); 130.92 (d,
6.30 28.92 39.00 71.70, PC C)
121.65, d, 40.45 (d, 16.34, PNCH3); 42.50 (s, NCH3); 122.60, (d,
10.0 34.0, C CCl2); 136.00 (d, 74.0, PC C)
16
CDCl3
C6D6
27
31.82, d,
7.54
30.40, d,
10.0
29
C6D6
158.20, d, 133.60, s
6.30
28
C6D6
30.91, s
157.78, d, 136.40, d, 117.45, d, 42.42 (s, NCH3); 126.80 (d, 42.75, C CCl2); 131.19
6.30 7.54 7.54 (d, 50.30, PC C)
159.07, d, 136.41, d, 117.34, d, 37.20 (d, 16.35, PNCH3); 42.34 (s, NCH3); 128.70 (d,
15.09 15.09 150.91 94.32, PC Cl; 130.68 (d, 17.61, C CCl2)
159.27, d, 138.30, d, 117.54, d, 42.27 (s, NCH3); 125.20 (d, 115.70, PC C); 134.64 (d,
13.80 17.60 153.40 17.60, C CCl2)
159.55, d, 137.76, d, 116.28, d, 42.19 (s, NCH3); 125.67 128.70 (d, 90.54, PC C);
12.57 16.35 128.27 132.60 (d, 17.60, C CCl2)
159.42, d, 138.64, d, 116.38, d, 42.10 (s, NCH3); 119.00 (s, 4-Ph); 123.27 (d, 18.86,
30
CDCl3
CDCl3
CDCl3
CDCl3
32.53, s
32.75, s
32.92, s
32.35, s
32a
32b
32c
13.83
17.60
152.17
2,6-Ph); 129.00 (s, 3,5-Ph); 129.40 (d, 56.60,
PC C); 132.18 (d, 16.35, C CCl2); 149.18 (s, i-Ph)
31
CDCl3
32.00, s
157.70, d, 136.57, d, 121.00, d, 37.45 (s, PNCH3); 40.30 (s, C CNCH3); 42.50 (s,
11.30
13.80
138.30
NCH3); 73.00 (d, 138.00, PC C); 165.25 (d, 24.00,
C CNCH3)
33a
33b
CDCl3
CDCl3
32.00, s
32.43, s
157.30, d, 135.80, d, 121.80, d, 39.90; 41.50 (s, C CNCH3); 42.20 (s, NCH3); 70.00
12.75 15.10 143.40 (d, 161.00, PC C); 164.35 (d, 20.10, C CNCH3)
158.00, d, 136.05, d, 120.20, d, 40.28; 42.00 (s, C CNCH3); 42.44 (s, NCH3); 68.05
11.30 15.09 123.24 (d, 132.00, PC C); 165.27 (d, 24.00, C CNCH3)
162.55, d, 144.67, d, 105.50, d, 11.00 (d, 60.40, P+CH3); 42.30 (s, NCH3); 119.90 (d,
34a CD3CN 34.37, s
12.75
15.10
120.73
93.00, i-PhP); 130.93 (d, 7.50, 3,5-PhP); 133.77 (d,
11.32, 2,6-PhP); 135.80 (d, 2.50, 4-PhP)
35a
35b
35c
CDCl3
CDCl3
CDCl3
32.52, s
32.88, s
34.25, s
158.64, d, 127.80, d, 120.90, d, 42.40 (s, NCH3); 131.52 (d, 110.60, i-Ph); 131.80 (d,
11.32
15.09
127.00
11.32, 2,6-Ph); 132.27 (d, 3.8, 4-Ph); 128.53 (d,
12.5, 3,5-Ph)
151.30, d, 140.06, d, 125.70, d, 15.43 (s, SCH3); 130.91(br s, i-Ph); 131.80 (d, 10.06,
11.32
15.09
123.20
2,6-Ph); 132.48 (d, 3.77, 4-Ph); 128.75 (d, 12.57,
3,5-Ph)
153.85, d, 140.24, d, 125.20, d, 129.25 (s, i-PhP); 120.07 (s, 2,6-Ph); 129.50 (s, 4-Ph);
8.8
16.36
121.98
128.73 (s, 3,5-Ph); 131.41 (d, 111.92, i-PhP); 131.70
(d, 10.06, 2,6-PhP); 132.38 (d, 2.5, 4-PhP); 128.60
(d, 10.06, 3,5-PhP)
36a
36b
CDCl3
CDCl3
32.60, s
33.04, s
159.03, d, 136.80,
11.32 (d, 13.8
151.54, d, 138.79, (s 124.00, d, 15.43 (s, SCH3); 128.8 (d, 12.6, 2,6-Ph); 131.05 (d,
119.40, d, 42.10 (s, NCH3); 128.6 (d, 12.6, 3,5-Ph); 131.3 (br s,
109.41 i-Ph); 132.0 (d, 8.8, 2,6-Ph); 132.1 (s, 4-Ph)
10.06
105.64
89.3, i-Ph); 132.03 (d, 12.6, 3,5-Ph); 132.27 (br s,
4-PhP);
36c
37b
CDCl3
CDCl3
34.42, s
32.50, s
154.3, d,
10.06
139.56, d, 123.85, d, 128.70 (d, 10.0, 3,5-PhP); 128.85 (s, 3,5-Ph); 129,22
15.09
105.64
(s, 2,6-Ph); 129.57 (s, 4-Ph); 129.64 (s, i-PhP);
131.48 (d, 89.3, i-PhP); 132.09 (d, 11.32, 2,6-PhP);
132.20 (d, 3,77, 4-PhP);
151.34, d, 141.15, d, 123.50, d, 15.30 (s, SCH3); 55.54 (s, OCH3); 114.45 (3,5-C-Ar);
8.80
13.80
105.64
123.35 (d, 17.60, 2,6-CPh); 128.77 (d, 13.80,
3,5-CPh); 130.85 (d, 109.50, i-CPh); 131.94 (s,
4-CPh); 132.00 (2,6-C-Ar); 144.00 (d, 2.50, i-C-Ar);
152.26 (s, 4-C-Ar)
(Continued)
Heteroatom Chemistry DOI 10.1002/hc

5-Phosphorylated 1,2-Disubstituted Imidazoles 301
TABLE 4 Continued
13C NMR
No
Solvent
CDCl3
N-CH3
C-2
C-4
C-5
Other Signals
37a
32.15, s
159.00, d, 138.63, d, 118.74, d, 42.45 (s, NCH3); 55.54 (s, OCH3); 114.40 (3,5-C-Ar);
11.30
13.80
110.64
123.25 (d, 17.60, 2,6-CPh); 128.65 (d, 12.75,
3,5-CPh); 131.80 (d, 2.50, 4-CPh); 131.22 (d,
109.50, i-CPh); 132.00 (d, 10.20, 2,6-C-Ar); 144.00
(d, 2.50, i-C-Ar); 152.26 (s, 4-C-Ar)
38a
38b
38c
CDCl3
CDCl3
CDCl3
34.73, s
36.05, s
35.73, s
150.95, d, 133.40, br 123.90, d, 37.50 (s, N+CH3); 42.13 (s, NCH3); 128.28 (s,
6.30
s
115.70
4-C-Ph); 128.50 (d, 113.20, i-C-Ph); 129.40 (d,
13.80, 2,6-C-Ph); 132.22 (d, 11.30, 3,5-C-Ph)
147.40, d, 133.33, d, 121.70, d, 19.43 (s, SCH3); 38.58 (s, N+CH3); 127.88 (d, 91.80,
5.00
3.80
106.90
i-C-Ph); 129.05 (d, 12.75, 3,5-C-Ph); 129.58 (d,
13.80, 2,6-C-Ph); 132.68 (d, 2.5, 4-C-Ph);
149.70, d, 132.22, d, 128.26, d, 37.86 (s, N+CH3); 120.05 (s, i-C-Ph); 128.20 (d,
5.00
17.60
114.45
110.70, i-C-PhP); 129.56 (d, 13.80, 3,5-C-PhP);
129.96 (s, 3,5-C-Ph); 131.20 (s, 2,6-C-Ph); 132.30
(d, 12.75, 2,6-C-PhP); 133.25 (s, 4-C-Ph); 133.64 (d,
3.80, 4-C-PhP)
38d CD3CN 34.35, s
150.97, d, 128.07, d, 123.42, d, 14.30 (s, PNCH2CH3); 35.97 (s, N+CH3); 39.44 (d,
8.80
145.93, d, 130.53, d, 131.57, d, 14.23 (s, PNCH2CH3); 19.21 (s, SCH3); 38.50 (s,
5.00 16.35 144.60
N+CH3); 40.54 (d, 3.80, PNCH2)
149.70, d, 130.90, d, 127.90, d, 36.97 (s, N+CH3); 37.37 (d, 5.00, CH3N); 121.66 (s,
18.90
182.35
3.80, PNCH2); 41.14 (s, NCH3)
38e
38f
CDCl3
35.63, s
CD3CN 35.76, s
5.00
17.60
149.65
i-C-Ph); 130.30 (s, 3,5-C-Ph); 131.53 (s, 2,6-C-Ph);
133.54 (s, 4-C-Ph)
accordingly, they require more severe conditions
for interaction with imidazoles 1a–c to form cor-
responding diphenyl(imidazol-5-yl)phosphines 7a–c
(Scheme 9 and Table 1). The readiness of the reac-
tion regularly decreases together with the electron-
donating ability of the 2-substituent in the imidazole
ring. Application of second mole of imidazole as HCl
acceptor is also reasonable to advance its purity.
Starting from compounds 7a–c a number of
phosphorus(V) derivatives 35–37 have been ob-
tained by standard procedures (Scheme 9). As evi-
denced by 31P NMR spectral data, phosphines 7a–c
are alkylated with CH3I not only at the phospho-
rus atom but also at the heterocyclic imine nitrogen
atom to form a mixture of compounds (δP(Py) 8–10
and 13–14 ppm, respectively) from which in the case
of 7a only we managed to isolate phosphonium salt
34a by crystallization.
EXPERIMENTAL
General
All procedures with air and moisture sensitive com-
pounds were performed under an atmosphere of
dry argon in flame-dried glassware. Solvents were
purified and dried by standard methods. Melting
points were determined with an electro-thermal cap-
illary melting point apparatus and were uncorrected.
Yields, crystallization solvents, and physical specifi-
cations of isolated products are listed in Table 2.
All reactions were carried out monitoring by 31P
NMR. All organic solutions were dried over anhy-
drous MgSO4. 1H spectra were recorded on a Bruker
Avance DRX 500 (500.13 MHz) or Varian VXR-300
(299.94 MHz) spectrometer. 13C NMR spectra were
recorded on a Bruker Avance DRX 500 (125.75 MHz)
spectrometer. 31P NMR spectra were recorded on a
Varian VXR-300 (121.42 MHz) spectrometer. Chem-
ical shifts (δ) are reported in ppm downfield rela-
N
N
S8; N3Ar
R
P
R
P
N
N
Y
3
3
Me
Me
21a–c Y = S
17a–c
22b, c Y = N-Ar
1
tive to internal TMS (for H, 13C) and external 85%
R = NMe2 (a), SMe (b), Ph (c)
Ar = C6H4-OCH3-p
H3PO4 (for 31P). Chromatography was performed on
silica gel Gerudan SI60. Elemental analyses were
performed at the Microanalytical laboratory of the
SCHEME 5
Heteroatom Chemistry DOI 10.1002/hc

302 Yurchenko et al.
N
N
N
Py
Ph
2 mol 1a
Ph
PhPCl2
+
2
R
P
Me2N
P
R
.
N
.
N
N
−1 HCl
−1a HCl
Cl
Me
2
Me
Me
24
23a–c
1a–c
R = NMe2 (a); SMe (b); Ph (c)
S8
N
Ph
Me2N
P
N
S
2
Me
25
SCHEME 6
Institute of the Organic Chemistry National
Academy of Sciences of Ukraine.
CCDC 643530 (8b), 693407 (19c), and 693406
(20c) contain the supplementary crystallographic
data for this paper. These data can be obtained free
of charge via www.ccdc.cam.ac.uk/conts/retrieving.
html (or from the Cambridge Crystallographic Data
Centre, 12, Union Road, Cambridge CB2 1EZ, UK;
N
N
N
Cl3C
CCl3PCl2
CCl4/ (Et2N)3P
P
Cl2P
NMe2
NMe2
N
NMe2
N
N
Et2O
Cl
Py
Me
Me
1a
Me
2a
26
SCHEME 7
N
N
Cl2C=CCl
Me2N
N
Cl2C=CCl
Me2NSiMe3
CCl2=CClPCl2
NMe2
P
P
NMe2
NMe2
N
N
N
Cl
2 mol 1a, Py
Me
27
Me
29
Me
1a
S8
N
N
Cl2C=CCl
Me2N
CCl2=CClPCl2
Cl2C=CCl
P
P
NMe2
N
NMe2
N
Me
28
4 mol 1a, Py
2
S
Me
30
4 Me2NH
H2O2; S8; PhN3
N
(Me2N)2C=CCl
Me2N
N
Cl2C=CCl
P
NMe2
N
P
NMe2
N
S
Me
31
X
2
Me
32a–c
Me2NH
N
(Me2N)2C=CCl
P
NMe2
N
X
2
Me
X=O (a), S (b), N-Ph (c)
33a, b
SCHEME 8
Heteroatom Chemistry DOI 10.1002/hc

5-Phosphorylated 1,2-Disubstituted Imidazoles 303
N
+
Ph2PHal
2
R
N
Me
1a–c
.
Py
−1 HCl
N
R
N3Ar
MeI
Ph2P
N
Ar = p-MeO-C6H4N3
Me
7a–c
H2O2
S8
N
N
N
N
I
+
Ph2P
N
Ar
R
Ph2P
R
Ph2P
R
R
Ph2P
N
N
N
N
S
O
Me
Me
Me
Me
Me
37a,b
35a–c
36a–c
34a
R = NMe2 (a), SMe (b), Ph (c)
Hal = Cl (a), Br (b, c)
SCHEME 9
fax: +44 1223 336033; or deposit@ccdc.cam.ac.
concentrated in vacuo. The residue was distilled in
vacuo to give 2d as a light yellow liquid.
uk).
General Procedure for Preparation of N,N,Nꢁ,Nꢁ-
Tetraalkyl-P-(1-methyl-2-(R)-1H-imidazol-5-
yl)phosphonous Diamide 3a–d
General Procedure for Preparation of 1-Methyl-
2-(R)-1H-imidazol-5-ylphosphonous Dihalides
2a–d
To a stirred solution of dichlorophosphine 2a–d
(10 mmol) in benzene (15 mL) cooled to 0–5◦C, a so-
lution of diethylamine (42 mmol) or dimethylamine
(for 2c) in benzene (20 mL) was added dropwise
over 10 min. The reaction mixture was stirred for
2 h (3 h for 2c) at 20◦C. The precipitate was filtered
off, washed with benzene (2 × 20 mL), and the fil-
trate was concentrated in vacuo. The residue was
distilled in vacuo to give 3a–d.
A solution of imidazole 1a–c (10 mmol) in pyridine
(20 mL) to phosphorus trichloride (or phosphorus
tribromide for 1c; 25 mmol) was added. The reaction
mixture was stirred for 2 h at 20◦C (1a), for 3 h (1b),
or 48 h at 100◦C (1c). Pyridine was removed in vacuo,
then benzene (or diethyl ether for 1a; 50 mL) was
added, and the resulted mixture was heated up to
reflux. The precipitate was filtered off, washed with
benzene (or diethyl ether for 1a; 2 × 20 mL), and the
filtrate was concentrated in vacuo. The residue was
distilled in vacuo to give 2a–d.
P-[2-(Dimethylamino)-1-methyl-1H-imidazol-5-
yl]-N,N-dimethylphosphonamidous Chloride 4
1-Methyl-2-phenyl-1H-imidazol-5-yl-phosphonous
dichloride 2d (Method B). To a solution of imida-
zole 1a (1.25 g, 10 mmol) and triethylamine (2.0 g,
20 mmol) in pyridine (20 mL), a mixture of phos-
phorus tribromide (2.7 g, 10 mmol) and phosphorus
trichloride (5.5 g, 40 mol) was added. The reaction
mixture was heated for 2 h at 120◦C. Pyridine was
removed in vacuo, and then diethyl ether (50 mL)
was added. The precipitate was filtered off, washed
with diethyl ether (2 × 20 mL), and the filtrate was
To dichlorophosphine 2a (2.3 g, 10 mmol), a so-
lution of N,N-dimethyltrimethylsilylamine (1.2 g,
10 mmol) in dichloromethane (15 mL) was added.
The reaction mixture was heated for 40 min at
100◦C in a sealed tube. The solvent was removed
in vacuo; the residue was treated with hot pentane
(2 × 10 mL), insoluble impurities were filtered off
and the filtrate was evaporated. The crude product
was distilled in vacuo to give pure 4 as a pale yellow
liquid.
Heteroatom Chemistry DOI 10.1002/hc

304 Yurchenko et al.
added. After stirring for 2.5 h at −40◦C, the reaction
mixture was allowed to warm to −10◦C and water
(5 mL) was added. The organic layer was separated
and concentrated in vacuo. The residue was treated
with hot hexane (2 × 50 mL). The solution was re-
fined with activated charcoal and concentrated to
40 mL. The precipitate formed at −10◦C was filtered
off and washed with hexane to give 7c as colorless
crystals.
P-(1,1-Dichloro-2,2,2-trifluoroethyl)-P-[2-
(dimethylamino)-1-methyl-1H-imidazol-5-yl]-
N,N-dimethylphosphinous Amide 5
To a stirred solution of compound 4 (2.4 g, 1 mmol)
and trifluorotrichloroethane (4.5 g, 2.4 mmol) in
diethyl ether (40 mL), tris(diethylamino)phosphine
(5.9 g, 2.4 mmol) in diethyl ether (15 mL) was added
dropwise at −60 to −80◦C over 20 min. The reaction
mixture was allowed to warm to 25◦C and stirred
for further 30 min. The precipitate was filtered off,
washed with diethyl ether (2 × 20 mL); the filtrate
was concentrated in vacuo. The oily residue was
treated with hot pentane (30 mL) to afford 5, pre-
cipitating at −7◦C as colorless crystals.
General Procedure for Preparation of P-[1-
Methyl-2-(R)-1H-imidazol-5-yl]-N,N,Nꢁ,Nꢁ-
tetraalkyl(thio)phosphonic Diamide 8a–d,
O,O-Diisopropyl [1-methyl-2-(R)-1H-imidazol-
5-yl](thio)phosphonate 8e, f, Tris(1-methyl-2-
phenyl-1H-imidazol-5-yl)phosphine Sulfide
21a–c, and Diphenyl(1-methyl-2-R-1H-
imidazol-5-yl)phosphine Sulfide 36a–c
General Procedure for Preparation of
Diisopropyl[1-methyl-2-(R)-1H-imidazol-5-
yl]phosphonite 6a,b
To a solution of compounds 3a–d, 6a,b, 17a–c, or
7a–c (1 mol) in benzene (or dichloromethane for
17a–c; 3 mL), powdered sulfur (1.1 mol) was added.
The mixture was stirred for 3–4 h at 20◦C (in case
35a–c), for 18 h (21a) or heated for 4 h (21b), or
for 14 h (21c) at 40◦C. Benzene (dichloromethane)
was removed in vacuo. The crude product was crys-
tallized from the appropriate solvent to give 8a–d,
8e,f, 21a, and 36a–c, respectively (see Table 1). In
the case of 21b,c, the product precipitated from the
concentrated diethyl ether solution (15 mL) prelim-
inarily refined with activated charcoal.
To a solution of dichlorophosphine 2a,b (10 mmol)
and triethylamine (21 mmol) in benzene (50 mL)
cooled to 0–5◦C, isopropanol cooled to −30◦C
(21 mmol) was added. The reaction mixture was
stirred for 15 h at 20◦C. The precipitate was filtered
off, washed with benzene (2 × 20 mL); the filtrate
was concentrated in vacuo, and the oily residue was
treated with pentane (70 mL). Insoluble impurities
were filtered off, and the filtrate was concentrated.
The residue was distilled in vacuo to give 6 a,b.
General Procedure for Preparation of
5-(Diphenylphosphino)-1-methyl-2-(R)-1H-
imidazole 7a–c
General Procedure for Preparation of P-[1-
Methyl-2-(R)-1H-imidazol-5-yl]-N,N,Nꢁ,Nꢁ-
Tetraethylphosphonic Diamide 10a–c
To a solution of 1a–c (22 mmol) in pyridine (30 mL),
Ph2PCl (for 1a), and Ph2PBr (for 1b, c; 10 mmol) was
added. The reaction mixture was stirred for 22 h
at 20◦C (for 1a), 8 days at 30◦C (for 1b), and 54 h
at 100◦C (for 1c). Pyridine was removed in vacuo,
then benzene (50 mL) was added, and the resulted
mixture was heated up to reflux, the precipitate was
filtered off, washed with benzene (2 × 25 mL), the
filtrate was concentrated in vacuo. The residue was
treated with hot hexane (60 mL); insoluble impuri-
ties were filtered off, and the filtrate concentrated.
The residue was distilled in vacuo to give 7a–c.
To a solution of compound 3a–c (1 mmol) in hex-
ane (25 mL), hexachloroethane (1 mmol) dissolved
in hexane (25 mL) was added. In 1 h, the intermedi-
ate chlorophosphonium chloride 9 was filtered off,
dissolved in dichloromethane (15 mL), and shaken
with a saturated solution of Na2CO3. The organic
layer was separated, washed with water, dried, and
concentrated in vacuo. The crude product was crys-
tallized from the appropriate solvent to give 10a–c.
General Procedure for Preparation of
Diisopropyl 2-(Dimethylamino)-1-methyl-1H-
imidazol-5-yl-phosphonate 10e,f, Tris(1-
methyl-2-R-1H-imidazol-5-yl)phosphine Oxide
19b,c, and Diphenyl(1-methyl-2-R-1H-imidazol-
5-yl)phosphine Oxide 35a–c
5-(Diphenylphosphino)-1-Methyl-2-Phenyl-1H-
imidazole 7c (Method B). To a stirred solution of
bromobenzene (3.2 g, 2 mmol) in THF (10 mL), BuLi
(0.8 mL; 2.5 N solutions in hexane) was added drop-
wise at −80◦C over 5 min. The mixture was stirred for
30 min at −60◦C, after cooling to −90◦C; a solution
of dichlorophosphine 2c (2.6 g, 1 mmol) in THF was
To a solution of compounds 6a,b, 17b,c, or 7a–
c (5 mmol) in dichloromethane (5 mL), hydrogen
Heteroatom Chemistry DOI 10.1002/hc

5-Phosphorylated 1,2-Disubstituted Imidazoles 305
peroxide (5 mmol, 30% solution) was added. The
reaction mixture was shaken for 15–30 min. The or-
ganic layer was separated, washed with water, dried,
and concentrated in vacuo affording the residue,
which in the case of 10f was distilled in vacuo to
give the target product or crystallized from the ap-
propriate solvent to give 10e, 19b,c, and 35a–c, re-
spectively.
phoramidous dichloride (1.46 g, 1 mmol) in pentane
(10 mL) at −90◦C was added dropwise. The reaction
mixture was allowed to warm up to −40◦C. After stir-
ring for further 3 h, ammonia (liquid; 2 mL) at −60◦C
was added. The reaction mixture was concentrated
in vacuo; the residue was treated with hot benzene
(60 mL). The precipitate was filtered off, washed
with benzene (2 × 20 mL), and the filtrate was
concentrated in vacuo. The residue was treated with
hot hexane (2 × 50 mL), insoluble impurities were
filtered off, and the filtrate was evaporated to 40 mL
to give 14, precipitating at −7◦C.
P-(1,1-Dichloro-2,2,2-trifluoroethyl)-P-[2-
(dimethylamino)-1-methyl-1H-imidazol-5-yl]-
N,N-dimethylphosphinic Amide 11
To a solution of 5 (2.4 g, 1 mmol) in pyridine (8 mL)
cooled to 0–5◦C, hydrogen peroxide (1 mmol, 30%
solution) was added. After stirring for 10–15 min,
pyridine was removed in vacuo; the residue was
quenched, and then crystallized from diethyl ether
(40 mL) to give 11 as colorless crystals.
Bis[2-(dimethylamino)-1-methyl-1H-imidazol-5-
yl]phosphinous Chloride 15
To phosphorus trichloride (1.65 g, 12 mmol) cooled
to −30◦C, a solution of 14 (3.20 g, 10 mmol) in ben-
zene (20 mL) was added. The reaction mixture was
allowed to warm to 20◦C and then heated for 15 min
at 50◦C. After cooling, benzene was removed in vacuo
and the residue was extracted with hot hexane (2 ×
60 mL). If needed, insoluble impurities were filtered
off; the filtrate was concentrated in vacuo to give the
crude product distilled in vacuo to give 15 as a yellow
liquid.
General Procedure for Preparation of
Bis(diethylamino)[1-methyl-2-(R)-1H-imidazol-
5-yl]methylphosphonium Iodide 12a,b and
[2-(Dimethylamino)-1-methyl-1H-imidazol-5-
yl](methyl)diphenylphosphonium Iodide 34a
To a solution of compound 3 a,b or 7a (1 mmol) in
benzene (5 mL), methyl iodide (1 mmol) was added.
The reaction mixture was stirred for 24 h at 20◦C.
Benzene was decanted; the oily residue was dried
in vacuo. Diethyl ether (15 mL) was added for so-
lidification (34a), followed by crystallization of the
obtained solid from ethyl acetate to give 12a,b.
Tris[2-(dimethylamino)-1-methyl-1H-imidazol-
5-yl]phosphine 17a
To phosphorus trichloride (1.50 g, 11 mmol), a solu-
tion of imidazole 1a (3.75 g, 30 mmol) and triethy-
lamine (3.0 g, 30 mmol) in pyridine (25 mL) was
added. The reaction mixture was stirred for 30 h
at 20◦C. Pyridine was removed in vacuo, and the
residue was heated up in benzene (75 mL) to reflux.
The precipitate was filtered off and washed with ben-
zene (2 × 20 mL). The filtrate was concentrated to
1/3 of volume. The precipitate formed under cooling
was filtered off and crystallized from diethyl ether
(60 mL) to give 17a as colorless crystals.
Isopropyl 2-(Dimethylamino)-1-methyl-1H-
imidazol-5-yl(methyl)phosphinate 13
To a solution of phosphonite 6a (2.73 g, 1 mmol)
in diethyl ether (25 mL), methyl iodide (0.16 g,
1.1 mmol) was added. The reaction mixture was
stirred for 18 days at 14–16◦C. The precipitate was fil-
tered off, and the filtrate concentrated in vacuo. The
residue was distilled in vacuo and was crystallized
from diethyl ether (5 mL) to give 13. The product is
highly hygroscopic.
Tris[1-methyl-2-(methylthio)-1H-imidazol-5-
yl]phosphine 17b and [1-Methyl-2-(methylthio)-
1H-imidazol-4-yl-]{bis[1-methyl-2-(methylthio)-
1H-imidazol-5-yl]phosphine 18b; Tris[1-methyl-
2-(methylthio)-1H-imidazol-5-yl]phosphine
Oxide 19b; [1-Methyl-2-(methylthio)-1H-
imidazol-4-yl]-{bis[1-methyl-2-(methylthio)-1H-
imidazol-5-yl]phosphine Oxide 20b
P,P-Bis[2-(dimethylamino)-1-methyl-1H-
imidazol-5-yl]-N,N-dimethylphosphinous
Amide 14
To a stirred solution of preliminarily dried over P2O5
imidazole 1a (2.5 g, 2 mmol) in THF (50 mL), t-
BuLi (1.2 mL, 1.7 N solutions in pentane) at −90◦C
was added dropwise over 15 min. After stirring for
1.5 h at −80 to −85◦C, a solution of dimethylphos-
To a solution of imidazole 1b (7.94 g, 62 mmol) in
pyridine (40 mL), phosphorus tribromide (2.71 g,
10 mmol) was added. The reaction mixture was
stirred for 4 days at 70◦C. Pyridine was removed in
Heteroatom Chemistry DOI 10.1002/hc

306 Yurchenko et al.
vacuo; the oily residue was heated up in benzene
(40 mL) to reflux. The precipitate was filtered off,
washed with benzene (2 × 20 mL), and the filtrate
was concentrated in vacuo. The residue was treated
with hot hexane (4 × 40 mL), the solution was con-
centrated in vacuo, and the solid residue crystallized
from diethyl ether (50 mL). Precipitate formed at −5
to −7◦C was filtered off in 24 h to give 17b. The di-
ethyl ether filtrate was concentrated, and the residue
was refined by chromatography on silica gel (eluent
EtOAc: CH3OH = 49:1) to give 18b (Rf = 0.55). To
a solution of the compounds with Rf = 0.38—0.45
in dichloromethane (2 mL) cooled to 0–5◦C, hydro-
gen peroxide (1 mL, 30% solution) was added. The
mixture was shaken for 10–15 min, the organic layer
was separated, washed with water, and dried and
concentrated to afford the residue, which was re-
fined by chromatography on silica gel (eluent CHCl3:
CH3OH = 49:1) to give 19b (Rf = 0.30) and 20b (Rf =
0.43).
to −30◦C, and degassed water was added. The or-
ganic layer was separated and concentrated to give
the oily residue, quenched and then treated with hot
diethyl ether (3 × 50 mL). The solution was con-
centrated to 30 mL to give 17c as colorless crystals
precipitating under cooling.
General Procedure for Preparation of
(4-Methoxyphenylimino)[tris(1-methyl-2-R-1H-
imidazol-5-yl)]phosphorane 22b,c and
Diphenyl(4-methoxyphenylimino)(1-methyl-2-R-
1H-imidazol-5-yl)phosphorane 37a,b
To a solution of compound 17b,c or 7 a,b (1 mmol)
in benzene (20 mL), a solution of 4-methoxyphenyl
azide (1 mmol) in benzene (10 mL) was added.
The reaction mixture was stirred for 15 min (22b),
30 min (37a), or 15 h (37 b) at 20◦C until nitrogen
stopped to evolving. In the case of 22c reflux for 1 h
at 80◦C is needed. Benzene was removed in vacuo,
and the residue was crystallized from diethyl ether to
give 22b,c. In the case of 37a,b, the oily residue was
treated with hot hexane (50 mL) to give the crude
product crystallized from the appropriate solvent.
Tris(1-methyl-2-phenyl-1H-imidazol-5-
yl)phosphine 17c and (1-Methyl-2-phenyl-1H-
imidazol-4-yl)-[bis(1-methyl-2-phenyl-1H-
imidazol-5-yl)phosphine Oxide 20c
General Procedure for the Preparation of
1-Methyl-2-(R)-1H-imidazol-5-
yl(phenyl)phosphinous Chloride 23a–c
To a solution of imidazole 1c (9.80 g, 62 mmol) in
pyridine (40 mL), phosphorus tribromide (2.71 g,
10 mmol) was added. The reaction mixture was
stirred for 7 days at 70◦C. Pyridine was removed
in vacuo; the oily residue was heated up in ben-
zene (40 mL) to reflux. The precipitate was filtered
off and washed with benzene (2 × 20 mL). The fil-
trate was concentrated to 10 mL, and the precipitate
formed under cooling was filtered and dried in vacuo
to give 17c. The filtrate was concentrated affording
the residue dissolved in hot benzene (10 mL). To a
solution obtained, hydrogen peroxide (3 mL, 30%
solution) was added. The mixture was shaken for
10–15 min, the organic layer was separated, washed
with water, and dried and concentrated to afford the
residue, which was refined by chromatography on
silica gel (eluent CHCl3:CH3OH = 1:9) to give 20c
(Rf = 0.38).
To a solution of imidazole 1a–c (10 mmol) in
pyridine (20 mL), phenylphosphonous dichloride
(20 mmol) was added. The reaction mixture was
stirred for 4 h at 20◦C (20a), for 48 h at 65◦C (20b), for
72 h at 130◦C (20c). Pyridine was removed in vacuo,
the oily residue was treated with diethyl ether (or
benzene for 20b,c; 70 mL), and the precipitate was
filtered off and washed with diethyl ether (benzene;
2 × 50 mL). The filtrate was concentrated in vacuo.
The residue was distilled to give 20a–c.
Bis[1-Methyl-2-(Dimethylamino)-1H-Imidazol-
5-yl](phenyl)phosphine Sulfide 25
A solution of imidazole 1a (0.25 g, 2 mmol) in pyri-
dine (5 mL) was added to 23a (0.27 g, 1 mmol).
The reaction mixture was heated for 30 min at 50◦C.
Then pyridine was removed in vacuo; the residue
was dried in vacuo and dissolved in benzene (10 mL).
Then powdered sulfur (0.035 g, 1.1 mmol) was
added. The reaction mixture was refluxed for 3 h.
After cooling, benzene was concentrated in vacuo
and the residue was treated with hot diethyl ether
(2 × 10 mL) to give 25 as yellow crystals precipitat-
ing under cooling.
Preparation of Tris(1-Methyl-2-Phenyl-1H-imida-
zol-5-yl)phosphine 17c (Method B). To a stirred so-
lution of imidazole 1c (2.37 g, 15 mmol) in THF
(30 mL), t-BuLi (8.82 mL, 1.7 N solutions in pen-
tane) was added dropwise at −95 to −98◦C in 20 min.
After stirring for 4 h at −80 to −90◦C, a solution
of phosphorus trichloride (0.69 g, 5 mmol) in THF
(5 mL) at −90 to −60◦C was added dropwise over
20 min. The reaction mixture was allowed to warm
Heteroatom Chemistry DOI 10.1002/hc

5-Phosphorylated 1,2-Disubstituted Imidazoles 307
the residue was treated with warm diethyl ether
(50 mL), the precipitate was filtered off, washed
with diethyl ether (2 × 30 mL), the filtrate was
concentrated in vacuo. The residue was treated
with hot hexane (2 × 40 mL); the residue after
hexane removal was distilled in vacuo to give 28 as
a colorless liquid.
General Procedure for Preparation of P,P-
Bis[2-(dimethylamino)-1-methyl-1H-imidazol-5-
yl]-N,N-dimethylphosphinic Amide 16 and
Bis[2-(dimethylamino)-1-methyl-1H-imidazol-5-
yl](trichlorovinyl)phosphine Oxide 32a
A solution of compound 14 or 28 (1 mmol) in
dichloromethane (5 mL) was shaken with hydrogen
peroxide (1.5 mmol, 30% solution) for 10–15 min.
The organic layer was separated off, washed with
water, and concentrated in vacuo. The residue was
treated with hot hexane (40 or 3 × 40 mL, respec-
tively) to give 16 as residue after hexane removal.
The solid residue of crude 32a precipitating from
hexane under cooling was recrystallized from diethyl
ether (40 mL). The precipitate formed at −7◦C was
filtered off and dried to give pure 32a.
P-[2-(Dimethylamino)-1-methyl-1H-imidazol-5-
yl]-N,N-dimethyl-P-(trichlorovinyl)phosphinous
Amide 29
To a solution of 27 (0.64 g, 2 mmol) in pen-
tane (10 mL) cooled to −10◦C, a solution of N,N-
dimethyltrimethylsilylamine (0.23 g, 2 mmol) in pen-
tane (50 mL) was added. The reaction mixture was
stirred for 2 h at 25◦C. Pentane was removed in
vacuo, and the residue was distilled twice in vacuo
to give 29 as a clear colorless liquid.
2-(Dimethylamino)-1-methyl-1H-imidazol-5-
yl(trichloromethyl)phosphinous Chloride 26
General Procedure for Preparation P-[2-
(Dimethylamino)-1-methyl-1H-imidazol-5-yl]-
N,N-dimethyl-P-(trichlorovinyl)phosphinothioic
Amide 30 and Bis[2-(dimethylamino)-1-methyl-
1H-imidazol-5-yl](trichlorovinyl)phosphine
Sulfide 32b
To a stirred solution of 2a (1.25 g, 10 mmol) and
carbon tetrachloride CCl4 (1.7 g, 11 mmol) in diethyl
ether (50 mL), tris(diethylamino)phosphine (2.72 g,
11 mmol) in diethyl ether (20 mL) was added drop-
wise at −60 to −80◦C over 20 min. The mixture was
allowed to warm to 20◦C and stirred for further 1.5 h
at 20◦C. The precipitate was filtered off, washed with
diethyl ether (2 × 20 mL), and the filtrate was con-
centrated in vacuo. The oily residue was treated with
hot pentane (50 mL). Insoluble impurities were fil-
tered off to give 26 as oil after solvent removal.
To a solution of compound 28, 29 (1 mmol) in ben-
zene (5 mL) powdered sulfur (1.1 mmol) was added.
The mixture was refluxed for 17 h (30) or 30 h (32b).
Benzene was concentrated in vacuo. The residue was
crystallized from pentane (10 mL) to give 30, or the
residue was treated with hot hexane (2 × 30 mL) and
then activated charcoal was added. The filtrate was
concentrated in vacuo to give 32b.
2-(Dimethylamino)-1-methyl-1H-imidazol-5-
yl(trichlorovinyl)phosphinous Chloride 27
To
trichlorovinyldichlorophosphine
(1.16
g,
Bis[2-(dimethylamino)-1-methyl-1H-imidazol-5-
yl](phenylimino)(trichlorovinyl)phosphorane
32c
5 mmol), a solution of imidazole 1a (1.25 g,
10 mmol) in pyridine (5 mL) cooled to −30 to −10◦C
was added. The reaction mixture was stirred for 3 h
at 20◦C. Then pyridine was removed in vacuo; the
oily residue was treated with pentane (2 × 40 mL).
The precipitate was filtered off and washed with
pentane (2 × 20 mL). The filtrate was concentrated,
and the residue was distilled in vacuo to give 27 as
a clear colorless liquid.
To a solution of 28 (1 mmol) in benzene (5 mL),
phenyl azide was added. The reaction mixture was
refluxed for 30 h. Benzene was removed in vacuo,
and the residue was treated with hot hexane (3 ×
40 mL) to give 32c as oil after solvent removal.
General Procedure for Preparation of 2-Chloro-
N,N,N,N-tetramethylethylene-1,1-diamino
Phosphorus(V) Derivatives 31, 33a,b
Bis[(2-(dimethylamino)-1-methyl-1H-imidazol-
5-yl)](trichlorovinyl)phosphine 28
To
trichlorovinyldichlorphosphine
(9.75
g,
A solution of compound 30, 32a,b (1 mmol) in
dimethylamine (2 g) was stirred for 3 days at
25◦C. Excess of dimethylamine was removed. The
residue was crystallized from pentane to give 31 or
treated hot hexane (2 × 20 mL) for 33a,b. Insoluble
42 mmol), a solution of imidazole 1a (1.25 g,
10 mmol) in pyridine (5 mL) cooled to −30 to −10◦C
was added. The reaction mixture was stirred for
5 h at 20◦C. Then pyridine was removed in vacuo;
Heteroatom Chemistry DOI 10.1002/hc

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impurities were filtered off. Hexane was removed in
vacuo to give 33a or crude 33b as solid residue, re-
crystallized from diethyl ether (10 mL).
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