Synthesis of novel macroheterocycles containing phosphorus and nitrogen

Article abstract of DOI:10.3184/030823407X256127

Synthesesofnovel3-[1-(4-chlorophenyl)ethyl]-1(indol-1-yl-methylphenyl- phosphinoylAhiophosphinoyl/selenophosphinoyl methyl)-1W-indole derivatives were accomplished in two steps. The synthetic route involves the cyclisation of equimolar quantities of 3-[4-chlorophenyl(1H-3-indolyl)methyl]-1H-indole (1) with bis(iodomethyl)phenylphosphine, bis(2-bromoethyl)phenylphosphine and tris-2-chloroethylphosphite (2a-c) in the presence of NaH under nitrogen atmosphere in dry THF to get P{III} intermediates (3a-c). These were further converted into the corresponding oxides, sulfides and selenides (4a-i) by reacting them with hydrogen peroxide, sulfur and selenium respectively.

Full text of DOI:10.3184/030823407X256127

598 RESEARCH PAPER
OCTOber, 598–601
JOUrNAL OF CHeMICAL reSeArCH 2007
Synthesis of novel macroheterocycles containing phosphorus and nitrogen
Boppudi Hari Babu, Kambam Srinivasulu, Gandavaram Syam Prasad and Chamarthi Naga Raju*
Department of Chemistry, Sri Venkateswara University, Tirupati-517 502, India
Synthesesofnovel3-[1-(4-chlorophenyl)ethyl]-1(indol-1-yl-methylphenyl-phosphinoyl/thiophosphinoyl/selenophosphinoyl
methyl)-1H-indole derivatives were accomplished in two steps. The synthetic route involves the cyclisation of
equimolar quantities of 3-[4-chlorophenyl(1H-3-indolyl)methyl]-1H-indole (1) with bis(iodomethyl)phenylphosphine,
bis(2-bromoethyl)phenylphosphine and tris-2-chloroethylphosphite (2a–c) in the presence of NaH under nitrogen
atmosphere in dry THF to get P(III) intermediates (3a–c). These were further converted into the corresponding
oxides, sulfides and selenides (4a–i) by reacting them with hydrogen peroxide, sulfur and selenium respectively.
Keywords: bis(iodomethyl)phenylphosphine, bis(2-bromoethyl)phenylphosphine, tris-2-chloroethylphosphite, macroheterocycle
Phosphorus-containing
macrocycles
are
interesting
Results and discussion
molecules with potential application in supramolecular and
synthetic organic chemistry.1 They have been synthesised
as phosphine oxides, phosphines, phosphates, phosphonates
and phosphoranes.2 The importance of these molecules,
as phosphorus analogues of crown ethers, is derived from
their potential catalytic activity and ion carrying properties.
The design of host molecules capable of binding neutral/
ionic metals as guests is an important area which is rapidly
expanding.3 Cram,4 Lehn,5 Vogtle,6 Majoral1 and others
and their coworkers have made significant advances
in this field of host–guest complexation.7 The past and
present research has led to the construction of phosphorus
macrocycles with large preorganised macrocyclic cavities
bearing concave functionalities.8 They are expected to function
as good hosts in ‘host–guest chemistry’. One-pot syntheses
of new macroheterocyclic phosphoranes were reported
from our research group9 with low yields under dilute
conditions. Template synthesis of 9-membered triphospha-
macrocycles with rigid o-phenylene backbone functions
was reported by Edwards and Whatton.10 In view of the
several possible applications and novelty in the chemistry of
host–guest molecular assemblies, it is thought worthwhile
to synthesise and study the properties of several phosphorus
macrocycles with nitrogen and phosphorus(III) as donor
atoms. These may also be of interest in the pharmaceutical
industry.
Syntheses of novel 3-[1-(4-chlorophenyl)ethyl]-1(indol-1-yl-
methylphenyl-phosphinoyl/thiophosphinoyl/selenophosphinoyl-
methyl)-1H-indole derivatives 4a–i were accomplished in two
steps. The synthetic route involves the cyclisation of equimolar
quantities of 3-[4-chlorophenyl(1H-3-indolyl)methyl]-1H-indole
(1) with bis(iodomethyl)/bis(2-bromoethyl)-phenylphosphine
and tris-2-chloroethylphosphite (2a–c) in the presence of
sodium hydride in dry tetrahydrofuran at 40–50°C in nitrogen
atmosphere to get the P(III) intermediates (3a–c). These were
further converted into the corresponding oxides, sulfides and
selenides (4a–i) by reacting them at 40–50°C with hydrogen
peroxide, sulfur and selenium respectively. Purification of
these macrocycles (4a–i) was achieved by filtering the reaction
mixture to separate the sodium iodide/sodium bromide/sodium
chloride. The filtrate was removed in a rotary evaporator to
obtain a residue. This was washed with water and crystallised
from ethanol. Physical data along with IR absorptions, elemental
analysis and 31P NMR data of 4a–i are given in Table 1.
All the compounds 4a–i exhibited characteristic IR
absorptions11-14 for (Table 1) P = O/S/Se, P–C(aliphatic) and P–O–
C(aliphatic) groups.
1
The H NMR spectra of 4a–i (Table 2) showed15,16 singlets
for H-2 and 6 at d 6.57–6.67. The triplets at d 6.67–6.96 and
d 7.12–7.18 are attributed to H-2' and 6' and H-3' and 5'
respectively. The aromatic protons of the indole moiety H-3a
and 5a, H-3b and 5b, H-3c and 5c and H-3d and 5d showed
Cl
Cl
Cl
4'
5'
6'
3'
2'
1'
5a
5d
3a
3d
4
3
5e
5f
5
3e
3f
5b
5c
3b
3c
H2O2 / S / Se
THF, 40-50 oC
2 NaH, THF
XY
+
2
6
P R
40-50 o
C
XY
7
N1
N
Y
N
Y
N
Y
N
H
N
H
Y
2a-c
P
1
P
R
4a-i
Z
R
Z = O / S / Se
3a-c
Compd.
X
Y
R
Compd.
Y
Z
R
Compd.
Y
Z
R
2"
3"
C6H5
CH2
CH2
C6H5
O
4f
CH2CH2
4a
4b
4c
Se
O
1"
2a
I
4"
5"
-CH2-
4g
CH2CH2O
-OCH2CH2Cl
S
C6H5
6"
4h
4i
Se
CH2CH2O
CH2CH2O
-CH2CH2-
S
C6H5
C6H5
-OCH2CH2Cl
-OCH2CH2Cl
2b
2c
CH2
Br
Cl
Se
CH2CH2
4d
4e
1"
2"
O
S
-CH2CH2O- -OCH2CH2Cl
CH2CH2
C6H5
Scheme 1
* Correspondent. E-mail: naga_raju04@yahoo.co.in
PAPER: 07/4823

JOUrNAL OF CHeMICAL reSeArCH 2007 599
Table 1 Physical IR and 31P NMR spectroscopic data of 4a–i
Compd M.p./°C Yielda/% Molecular
Elemental analysis calcd.
(found)
IR/cm-1
31P NMRb,c
data/ppm
no.
formula
C
H
N
P =
P–C(aliphatic)/
O/S/Se P–O–C(aliphatic)
4a
4b
4c
4d
4e
4f
121–123
134–135
118–119
104–105
112–114
129–130
114–115
127–128
139–140
53
62
58
67
57
70
68
65
59
C31H24N2OPCl
C31H24N2PSCl
73.4
(73.5
71.2
(71.25
65.3
(65.4
74.1
(74.1
72.0
(71.9
66.3
(66.2
61.15
(61.2
59.5
(59.4
55.1
(55.1
4.7
4.7
4.6
4.6
4.2
4.2
5.2
5.3
5.1
5.1
4.7
4.65
4.8
4.7
4.6
4.65
4.3
4.3
5.5
1274
774
771
762
21.23
33.18
69.61
27.12
54.38
63.19
9.32
5.55)
5.35)
5.3
C31H24N2PSeCl
C33H28N2OPCl
C33H28N2PSCl
4.9
5.0)
5.2
5.2)
5.1
5.1)
4.7
4.65)
4.9
4.95)
4.8
4.8)
4.4
4.4)
628
768
1279
776
754
788
C33H28N2PSeCl
C29H27N2O4PCl2
C29H27N2O3PSCl2
C29H27N2O3PSeCl2
621
769
4g
4h
4i
1278
771
1136
1148
1139
19.12
25.17
623
aRecrystallised from ethanol.
bRecorded in CDCl3
cChemical shifts in ppm from 85% phosphoric acid.
Table 2 1H NMR spectroscopic dataa,b of 4a–i
4a
4b
4c
4d
4e
4f
d = 5.93 (s, 1H, –CH), 6.60 (s, 2H, ArH), 6.96 (t, 2H, J = 5.8 Hz, ArH), 7.12 (t, 2H, J = 5.8 Hz, ArH), 7.20–7.34 (m, 8H, ArH),
5.58–5.81 (m, 4H, N–CH2), 7.51–7.62 (m, 5H, ArH)
d = 5.87 (s, 1H, –CH), 6.61 (s, 2H, ArH), 6.84 (t, 2H, J = 5.6 Hz, ArH), 7.18 (t, 2H, J = 5.6 Hz, ArH), 7.26–7.32 (m, 8H, ArH),
5.54–5.77 (m, 4H, N–CH2), 7.42 – 7.56 (m, 5H, ArH)
d = 5.90 (s, 1H, –CH), 6.58 (s, 2H, ArH), 6.92 (t, 2H, J = 5.7 Hz, ArH), 7.15 (t, 2H, J = 5.7 Hz, ArH), 7.22–7.30 (m, 8H, ArH),
5.59–5.80 (m, 4H, N–CH2), 7.46–7.58 (m, 5H, ArH)
d = 5.91 (s, 1H, –CH), 6.62 (s, 2H, ArH), 6.87 (t, 2H, J = 5.6 Hz, ArH), 7.16 (t, 2H, J = 5.8 Hz, ArH), 7.24–7.34 (m, 8H, ArH),
5.05–5.12 (m, 4H, N–CH2), 2.16–2.22 (m, 4H, –CH2–PO), 7.39–7.51 (m, 5H, ArH)
d = 5.86 (s, 1H, –CH), 6.67 (s, 2H, ArH), 6.87 (t, 2H, J = 5.6 Hz, ArH), 7.14 (t, 2H, J = 5.7 Hz, ArH), 7.21–7.32 (m, 8H, ArH),
5.09–5.14 (m, 4H, N–CH2), 2.19–2.23 (m, 4H, –CH2–PO), 7.39–7.51 (m, 5H, ArH)
d = 5.90 (s, 1H, –CH), 6.57 (s, 2H, ArH), 6.76 (t, 2H, J = 5.4 Hz, ArH), 7.12 (t, 2H, J = 5.5 Hz, ArH), 7.25–7.33 (m, 8H, ArH),
5.07–5.13 (m, 4H, N–CH2), 2.18–2.22 (m, 4H, –CH2–PO), 7.38–7.52 (m, 5H, ArH)
4g
4h
4i
d = 5.88 (s, 1H, –CH), 6.58 (s, 2H, ArH), 6.79 (t, 2H, J = 5.5 Hz, ArH), 7.15 (t, 2H, J = 5.7 Hz, ArH), 7.23–7.34 (m, 8H, ArH),
5.11–5.18 (m, 4H, N–CH2), 4.29–4.63 (m, 4H, N–CH2–CH2OP), 4.23 (t, 2H, –OCH2CH2Cl), 3.53 (t, 2H, –CH2Cl)
d = 5.87 (s, 1H, –CH), 6.64 (s, 2H, ArH), 6.93 (t, 2H, J = 5.8 Hz, ArH), 7.16 (t, 2H, J = 5.8 Hz, ArH), 7.24–7.31 (m, 8H, ArH),
5.14–5.17 (m, 4H, N–CH2), 4.29–4.64 (m, 4H, N–CH2CH2OP), 4.21 (t, 2H, –OCH2CH2Cl), 3.54 (t, 2H, –CH2Cl)
d = 5.84 (s, 1H, –CH), 6.61 (s, 2H, ArH), 6.90 (t, 2H, J = 5.7 Hz, ArH), 7.15 (t, 2H, J = 5.8 Hz, ArH), 7.23–7.31 (m, 8H, ArH),
5.12–5.16 (m, 4H, N–CH2), 4.27–4.61 (m, 4H, N–CH2CH2OP), 4.23 (t, 2H, –OCH2CH2Cl), 3.51 (t, 2H, –CH2Cl)
aRecorded in DMSO.
bChemical shifts in ppm and J (Hz) in parenthesis.
complex multiplets in the region d 7.20–7.34. The bridging
methyne proton (H-4) showed a singlet at d 5.84–5.91. The
protons of the aromatic moiety linked at phosphorus in 4a–f
resonated as multiplets in the region d 7.38–7.62. The protons of
N–CH2(C-8) gave a multiplet due to coupling with phosphorus
in the region d 5.54–5.81 in compounds, 4a–c. A multiplet in
the region d 5.04–5.14 (4H) is assigned to –NCH2 protons in
compounds 4d–f, whereas –CH2–P(O)/S/Se protons resonated
upfield as a multiplet (4H) in the range of d 2.16–2.23 in 4d–f.
In compounds, 4g–i two multiplets appeared one at d 5.11–5.18
and the other at d 4.29–4.64 for –N–CH2 and –CH2–O–P(O/
Se/Se) respectively. The exocyclic P–O–CH2–CH2–Cl moiety
gave two triplets for each methylene proton, one at d 4.21–4.23
(OCH2) and the other at d 3.51–3.53 (–CH2–Cl) as expected.
The 13C NMR spectra (Table 3) were recorded17,18 for a few
of the title compounds (4c, 4e and 4g). The bridged methyne
carbon (C-4) resonated upfield as a singlet in the range of
35.0–36.9 ppm due to its aliphatic nature and steric
environment. In compound 4c, the methylene carbon, P–
CH2–N, resonated18b as a doublet at d 44.2(d, 1Jp-c = 136 Hz).
In compound 4e, the N-CH2 methylene carbon gave a doublet
at d 35.0 (d, 2Jpcc = 4.2 Hz) and the P-CH2 carbon resonated
as a doublet at d 44.5 (d, 1Jpc = 132 Hz) due to coupling with
phosphorus. In 4g, the N–CH2– carbon signal appeared as a
doublet at d 35.6 (d, J = 4.7 Hz). The carbon of P–O–CH2–
resonated downfield as a doublet at d 61.3 (d, 2Jpoc = 5.1 Hz).
The exocyclic P–O–CH2– moeity gave a doublet at d 63.5 (d,
2Jpoc = 4.3 Hz) and –CH2–Cl resonated as a singlet at d 42.8.
31P NMR spectra of all the compounds 4a–i showed only one
phosphorus signal in the range of 9.32–69.61 ppm depending
on the elements present at phosphorus.19
Experimental
All reactions were carried out under anhydrous conditions under
a
nitrogen atmosphere. Melting points were determined with
open capillary tubes using Mel-temp apparatus. Elemental
a
analyses were performed by the Central Drug Research Institute,
Lucknow, India. All Ir spectra were recorded as Kbr pellets on a
1
Perkin-Elmer 1430 instrument, H, 13C and 31P NMR spectra were
recorded on AMX 400 MHz spectrometer, operating at 400 MHz for
1H, 100 MHz for 13C and 161.9 MHz for 31P as solutions in CDCl3
and the chemical shifts were referenced to TMS (1H and 13C) and
85% H3PO4 (31P).
PAPER: 07/4823

600 JOUrNAL OF CHeMICAL reSeArCH 2007
Table 3 13C NMR chemical shiftsa,b of some members of 4c, 4e and 4g
Compd no.
d
4c
140.3 (s, 2C, C-2 & 6), 124.1 (s, 2C, C-3 & 5), 35.0 (s, 1C, C-4), 121.4 (s, 2C, C-3a & 5a), 122.1 (s, 2C, C-3b & 5b), 123.6
(s, 2C, C-3c & 5c), 116.8 (s, 2C, C-3d & 5d), 152.6 (s, 2C, C-3e & 5e), 153.0 (s, 2C, C-3f & 5f), 44.2 (d, J = 136 Hz, 2C,
C-8 & 10, P–CH2–N), 140.3 (s, 1C, C-1'), 129.1 (d, J = 10.1 Hz, 2C, C-2' & 6'), 126.2 (s, 2C, C-3' & 5'), 135.8 (s, 1C, C-4'),
134.8 (s, 1C, C-1''), 127.8 (d, J = 9.3 Hz, 2C, C-2'' & 6''), 129.6 (s, 2C, C-3'' & 5''), 133.1 (s, 1C, C-4'')
4e
4g
140.7 (s, 2C, C-2 & 6), 123.8 (s, 2C, C-3 & 5), 36.9 (s, 1C, C-4), 120.2 (s, 2C, C-3a & 5a), 122.4 (s, 2C, C-3b & 5b), 123.9
(s, 2C, C-3c & 5c), 115.8 (s, 2C, C-3d & 5d), 151.4 (s, 2C, C-3e & 5e), 152.9 (s, 2C, C-3f & 5f), 35.0 (d, J = 4.2 Hz, 2C,
C-8 & 12, P–CH2–CH2–N), 44.5 (d, J = 132 Hz, 2C, C-9 & 11, P–CH2), 128.6 (s, 2C, C-2' & 6'), 127.5 (s, 2C, C-3' & 5'),
131.5 (s, 1C, C-4'), 129.5 (s, 1C, C-1''), 128.4 (d, J = 9.1 Hz, 2C, C-2'' & 6''), 128.8 (s, 2C, C-3'' & 5''), 129.3 (s, 1C, C-4'').
141.4 (s, 2C, C-2 & 6), 124.6 (s, 2C, C-3 & 5), 35.7 (s, 1C, C-4), 121.8 (s, 2C, C-3a & 5a), 122.6 (s, 2C, C-3b & 5b), 123.6
(s, 2C, C-3c & 5c), 117.4 (s, 2C, C-3d & 5d), 151.6 (s, 2C, C-3e & 5e), 153.2 (s, 2C, C-3f & 5f), 35.6 (d, J = 4.7 Hz, 2C,
C-8 & 14, N–CH2), 61.3 (d, J = 5.1 Hz, 2C, C-9 & 13, P–O–CH2), 133.3 (s, 1C, C-1'), 128.4 (s, 2C, C-2' & 6'), 127.1 (s, 2C,
C-3' & 5'), 130.7 (s, 1C, C-4'), 63.5 (d, J = 4.3 Hz, 1C, C-1''), 42.8 (s, 1C, C-2'')
aRecorded in CDCl3.
bChemical shifts in ppm and J (Hz) in parenthesis.
Table 4 Mass spectroscopic data of 4c, 4e and 4g
Compd no.
m/z (relative abundance)
4c
571 (M+∑ + 1, 12), 570 (M+∑, 10), 537 (15), 521 (2), 491 (16), 457 (21), 445 (14), 427 (13), 404 (7), 391 (2), 381 (6),
357 (13), 355 (34), 337 (6), 314 (16), 312 (23), 284 (6), 271 (10), 253 (23), 223 (8), 222 (14), 221 (100), 211 (18),
192 (19), 174 (38), 156 (21), 137 (4), 129 (22), 116 (7).
4e
4g
552 (M+∑ + 1, 8), 551 (M+∑, 5), 542 (6), 512 (13), 510 (21), 413 (3), 411 (9), 371 (3), 369 (7), 349 (2), 314 (8), 312 (24),
294 (2), 293 (12), 284 (7), 244 (2), 243 (9), 242 (100), 216 (3), 195 (2), 194 (8), 192 (26), 183 (2), 174 (6), 156 (6),
129 (19), 116 (11).
570 (M+∑ + 1, 2), 569 (M+∑, 4), 529 (4), 496 (6), 483 (4), 465 (2), 448 (10), 447 (5), 406 (3), 404 (11), 395 (9), 391 (3),
379 (5), 363 (17), 347 94), 336 (2), 318 (7), 317 925), 312 (36), 303 (8), 285 (10), 285 (10), 284 (39), 271 (28), 253 95),
239 (8), 238 (53), 236 (58), 235 (4), 213 (14), 194 (31), 192 (100), 174 (28), 156 (3), 135 (7), 116 (15).
Compound 1 was prepared by adopting the reported15 procedure.
Tris 2-chloroethyl phosphite (2c) was procured from Sigma-
Aldrich Chemical Company, Inc, USA and was used without further
purification.
was kept stirring and diiodomethane (5.35 g, 0.02 mole) in dry
THF (10 ml) was added at 10–15°C over 10 min. To this mixture,
dichlorophenylphosphine (1.79 g, 0.01 mole) in dry THF (10 ml) was
added dropwise from a dropping funnel. When the reaction started
the temperature increased to 40–45°C. Stirring of the mixture was
continued until the magnesium metal was completely dissolved to
form bis(iodomethyl)phenylphosphine.
Preparation of bis (2-bromoethyl) phenylphosphine (2b): In a dry
100 ml three necked flat-bottomed flask, fitted with dropping funnel,
a reflux condenser fitted with a calcium chloride tube, an inlet for
dry nitrogen and a thermometer were placed magnesium turnings
(0.48 g, 0.02 mole) and 10 ml of dry THF. The reaction mixture
was kept stirring and 1,2-dibromoethane (3.76 g, 0.02 mole) in dry
THF (20 ml) was added at 5–10°C over 10 min. To this mixture
dichlorophenylphosphine (1.79 g, 0.01 mole) in dry THF (10 ml) was
added dropwise from a dropping funnel. When the reaction started
the temperature was increased to 50–55°C. Stirring of the mixture
was continued until the magnesium metal was completely dissolved
to form bis(2-bromoethyl)phenylphosphine (2b).
Synthesis of phosphorus and nitrogen macroheterocyclic compound
(4a): A solution of bis (iodomethyl)phenylphosphine (2a) (0.39 g,
0.001 mole) in dry THF (15 ml) was added slowly to a solution of
3-[4-chlorophenyl(1H-3-indolyl)methyl]-1H-indole 1 (0.356 g, 0.001
mole) and sodium hydride (0.048 g, 0.002 mole) in dry THF (30 ml) at
0°C. After completion of the addition, the temperature of the reaction
mixture was raised to 40–50°C and the mixture was stirred for one
hour to form the trivalent P(III) intermediate, 3a. The progress of
the reaction was judged by the TLC analyses of the reaction mixture
using n-hexane and ethyl acetate (4:1) on silica gel. The precipitated
sodium iodide was separated by filtration under nitrogen atmosphere.
Hydrogen peroxide (30% H2O2, 0.04 ml, 0.001 mole) was added to it
dropwise at 0–5°C. The reaction mixture was brought to 40–50°C and
kept with stirring for 2 h for the completion of oxidation as indicated
by TLC analyses. The solvent was evaporated in a rotary evaporator.
The resulting crude product was crystallised from ethanol to yield
0.26 g (53%) of 4a, m.p. 121–123°C.
Synthesis of phosphorus and nitrogen macroheterocyclic
compounds (4e) and (4f): A solution of bis (2-bromoethyl)phenyl-
phosphine (2b, 0.32 g, 0.001 mole) in dry THF (20 ml) was added
slowly to a solution of 3-[4-chlorophenyl(1H-3-indolyl) methyl]-
1H-indole 1 (0.356 g, 0.001 mole) and sodium hydride (0.048 g,
0.002 mole) in dry THF (30 ml) at 0°C. After completion of the
addition, the temperature of the reaction mixture was raised to
50–55°C and the mixture was stirred for 3 hours to form the trivalent
P(III) intermediate, 3b. The progress of the reaction was judged by the
TLC analyses of the reaction mixture using n-hexane and ethylacetate
(7:3) on silica gel. The precipitated sodium bromide was separated by
filtration under a nitrogen atmosphere. To the filtrate sulfur/selenium
(0.001 mole) in THF (20 ml) was added dropwise at 5–10°C.
The reaction mixture was brought to reflux and kept with stirring
for 2 h for the completion of reaction as indicated by TLC analysis.
The solvent was evaporated in a rotary evaporator. The resulting
crude product (4e/4f) obtained was crystallised from ethanol.
Synthesis of the other compounds 4b–d and 4g–i was achieved by
adapting the above procedure.
The authors are thankful to Prof. C. Devendranath Reddy and
Dr C. Suresh reddy, Department of Chemistry, S.V. University,
Tirupati, India for encouragement and to the Director, CDRI,
Lucknow, India for spectroscopic recording.
Received 8 October 2007; accepted 20 October 2007
Paper 07/4872
doi: 10.3184/030823407X256127
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Preparation of bis (iodomethyl)phenylphosphine (2a): In a dry
100 ml three necked flat-bottomed flask, fitted with dropping funnel,
a reflux condenser fitted with a calcium chloride tube, an inlet for
dry nitrogen and a thermometer were placed magnesium turnings
(0.48 g, 0.02 mole) and dry THF (10 ml). The reaction mixture
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