Microwave-assisted synthesis and sublimation enthalpies of hemiporphyrazines

Article abstract of DOI:10.1142/S1088424619500263

It was established that microwave irradiation solvent-free processing of 2,6- diaminopyridine or 1,3-phenylenediamine with phthalonitrile or 4-tert-butylphthalonitrile led to corresponding hemiporphyrazines with sufficiently high yields and a huge reduction in the time required for synthesis, from 8-12 h to 20 min. The data of IR and UV-vis spectroscopies and elemental analysis of the final products were found to be similar to those described in literature. The obtained hemiporphyrazines were characterized by 1H and 13C NMR data. We applied the Knudsen effusion method with mass spectrometric control of vapor composition. The mass spectrometric investigations established that the macrocyclic compounds give a stable stream of particles and their enthalpies of sublimation were estimated by the second law of thermodynamics.

Full text of DOI:10.1142/S1088424619500263

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2019; 23: 296–302
DOI: 10.1142/S1088424619500263
Published at http://www.worldscinet.com/jpp/
Microwave-assisted synthesis and sublimation
enthalpies of hemiporphyrazines
Aleksandra S. Kuznetsova, Nadezhda L. Pechnikova,Yuriy A. Zhabanov*,
Aleksey E. Khochenkov, Oscar I. Koifman, Victor V. Aleksandriiskii
and Mikhail K. Islyaikin*
Ivanovo State University of Chemistry and Technology, Research Institute of Macroheterocycles, IRLoN,
Sheremetevskiy Avenue, 7, Ivanovo 153000, Russia
Received 23 January 2019
Accepted 11 February 2019
ABSTRACT: It was established that microwave irradiation solvent-free processing of 2,6-
diaminopyridine or 1,3-phenylenediamine with phthalonitrile or 4-tert-butylphthalonitrile led to
corresponding hemiporphyrazines with sufficiently high yields and a huge reduction in the time
required for synthesis, from 8–12 h to 20 min. The data of IR and UV-vis spectroscopies and elemental
analysis of the final products were found to be similar to those described in literature. The obtained
1
hemiporphyrazines were characterized by H and 13C NMR data. We applied the Knudsen effusion
method with mass spectrometric control of vapor composition. The mass spectrometric investigations
established that the macrocyclic compounds give a stable stream of particles and their enthalpies of
sublimation were estimated by the second law of thermodynamics.
KEYWORDS: hemiporphyrazine, carbahemiporphyrazine, microwave-assisted synthesis, sublimation
enthalpy.
[8]. Various aspects of geometry and electron structure
INTRODUCTION
and relationship “structure-properties” of Hps are
Since their discovery [1], hemiporphyrazines [2]
the objectives of manifold detailed studies [9–12].
(Hps) have been attracting steady scientific and practical
Hemiporphyrazines are demonstrated to be a good
interest [3–6]. They can be considered as derivatives
platform for structural modifications to both central
of phthalocyanine (Pc) [7] where two opposite-faced
core and periphery of the macrocycles [13–18] that
isoindole rings (B) are replaced by rests of aromatic
allows for fine tuning of their properties. Thus Hps
diamines (A) in order to form anABAB-type macrocyclic
and their metallocomplexes reveal various practically
system. This structural modification interrupts the
useful properties [19–24] and are of special interest as
conjugation in the inner aromatic macrosystem which
optical limiters [25, 26] and excitonic luminescence [27],
is characteristic of blue-colored phthalocyanines and
nonlinear optical and photoelectronic materials [28–30].
leads to hypsochromically shifted yellow-orange Hps
The general method of synthesizing of hemipor-
phyrazines is a crossover-condensation of phthalonitrile
*Correspondence to: Yuriy A. Zhabanov, Ivanovo State
or its derivatives with carbo- or heterocyclic diamines
University of Chemistry and Technology, Physics department,
[1, 2, 9, 13, 23]. The protons donating organic solvents,
Sheremetevskiy Avenue, 7, Ivanovo 153000, Russia, tel.: +7
such as butyl alcohol, ethoxy ethanol, ethylene glycol,
(4932) 359874, fax: +7 (4932) 417995, email: zhabanov@isuct.
phenol and others, are used for this purpose. As a rule,
ru; Mikhail K. Islyaikin, Ivanovo State University of Chemistry
a complicated mixture of various products results
in separation of the main products from the reaction
mixture that seems to be a tedious task. Thus, solvents
and Technology, Fine Organic Synthesis Department,
Sheremetevskiy Avenue, 7, Ivanovo 153000, Russia, email:
islyaikin@isuct.ru.
Copyright © 2019 World Scientific Publishing Company

MICROWAVE-ASSISTED SYNTHESIS AND SUBLIMATION ENTHALPIES OF HEMIPORPHYRAZINES
297
used for synthesis, long duration of heating (8–12 h) and
multistep purification of target compounds are the main
difficulties of these approaches.
III Bruker 500 NMR spectrometer in DMSO-D6 or CDCl3
with operating frequencies of protons of 500 MHz and on
carbon 126 MHz. Chemical shifts are expressed in parts
per million (ppm), and coupling constants (J) in Hertz
(Hz). All reactions were performed using CEM-Discover
monomode equipment with systems of continuous supply
of microwave radiation (the power supply was set by an
operator in a range of 0–300 W) and magnetron frequency
2455 MHz in open vessels under solvent-free conditions.
Temperatures in the range 25–250°C, evaluated by
infrared detection, were maintained constant throughout
the reaction by modulation of emitted MW power. The
mass spectrometric study of the process of sublimation
of 5–8 by the Knudsen method was carried out using a
MI-1201 commercial magnetic sector mass spectrometer
modified for thermodynamic studies. The solid sample
was evaporated from a stainless steel effusion cell. The
ratio of the cross-section area of the cell to the effusion
aperture area was about 1000. The cell temperature was
measured by a tungsten-rhenium thermocouple W-Re
5/20. Mass spectra were recorded in vacuum no more
than 10-7 Torr and at an ionization energy of 36 eV for 5
(C26N8H16) and 8 (C36N6H34); 39 eV for 7 (C34N8H32) and
50 eV for 6 (C28N6H18). Accelerating voltage was 5 kV
Alternatively, microwave initialization seems to be an
effective approach that reduces the number of difficulties.
The effectiveness of microwave-assisted synthesis for
various fields of organic chemistry has been recently
reviewed [31, 32]. The main reasons to use microwave
initialization are a huge shortening of reaction duration
and the possibility of using a solvent-free protocol that
improves safety aspects and could be viewed as a green
chemistry approach.
Successful applications of microwave irradiation
(MWI) in porphyrins and phthalocyanines chemistry
have been reported in a number of works [33–37].
However, to the best of our knowledge, an application of
microwave irradiation to preparation of Hps has not yet
appeared in the literature.
Initially, sublimation in vacuum for purification of
hemiporphyrazines and their metal complexes was
described in pioneering works dedicated to the synthesis
of Hps [1, 38]. Later this method was developed [39] and
applied to deposition of tin layers upon surfaces in order to
studyelectro-andphotophysicalpropertiesofHps. Despite
their large applicability, the quantitative characteristics of
their sublimation ability remain unknown.
Therefore, the target of this work is to study the
principal applicability of microwave irradiation to the
synthesis of hemiporphyrazine, carbahemiporphyrazine
and their tert-butyl analogs and to provide quantitative
estimation of their enthalpies of sublimation.
for all compounds. Cathode emission current was Iemis
=
0.5 mA. The mass spectra were recorded in vapor
temperature ranges of 469–531 К (5), 464–525 К (6),
486–516К(7)and441–481К(8).Themassspectrometric
investigations established that all compounds give a stable
stream of particles. All four mass spectra show high-
intensity lines for molecular ions. No ions corresponding
to oligomeric species were detected.
EXPERIMENTAL
Synthesis
General procedure. A mixture of equimolecular
quantities of 2,6-diaminopyridine (1) or 1,3-phenyle-
nediamine (2) and phthalonitrile (3) or tert-butylphth-
alonitrile (4) was fine-milled in an agate pounder and
heated at 150°C for 20 min in a focused-microwave oven
with dynamic power not more than 100 W in open vessels
with the solvent-free protocol. After purification, selected
with respect of the solubility and as described below, the
substances 5–8 were finally dried under reduced pressure
at 130°C for 4 h.
5,26:13,18-Diimino-7,11:20,24-dinitrilo-[c,n]-
dibenzo-1,6,12,17-tetraazacyclodocosene-[1,3,5,7,9,-
12,14,16,21,23]-decene (5) was synthesized following the
general procedure by interaction of 0.12 g (0.93 mmol)
phthalonitrile and 0.1 g (0.93 mmol) 2,6-diaminopyridine.
The low-molecular products were isolated by column
chromatography on silica gel (ethyl acetate:hexane = 3:1)
and the target product was obtained by recrystallization
from benzyl alcohol. Final drying in vacuum resulted in an
orange product with yield 0.06 g, 29% (38% [1]). Melting
point: 346–347°C (344°C [1]). UV-vis, lmax, nm (loge),
(DMF): 352 (4.22) (354 (4.31) [1]). IR (KBr): n, cm-1:
Materials and methods
2,6-Diaminopyridine(1)and1,3-phenylenediamine(2)
were purified by recrystallization from dichloromethane
and dried under reduced pressure at 60°C for 4 h.
Phthalonitrile (3) was purified by recrystallization from
acetone and dried under reduced pressure at 60°C for
4 h. 4-tert-Butylphthalonitrile (4) was prepared following
the method described in the literature [40]. Column
chromatography was conducted on silica gel (Merck-60).
Thin-layer chromatography (TLC) was performed on
aluminum sheets precoated with aluminum oxide 60 F254
(Merck). Melting points were recorded on a JiaHang
Instruments apparatus in open capillary tubes. MALDI-
TOF spectra were obtained with Shimadzu Biotech
Axima Confidence in using a positive ion field without
matrix. The test for carbon, nitrogen and hydrogen was
carried out with a FlashEA 1112 CHNS–O Analyzer.
UV-vis spectra were recorded on a HITACHI U-2001
at room temperature in quartz cuvettes (l = 10 mm).
IR spectra were recorded on an Avatar 360 FT-IR
spectrometer. NMR spectra were recorded on an Avance
Copyright © 2019 World Scientific Publishing Company
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298
A. S. KUZNETSOVA ET AL.
690, 771, 1099, 1152, 1231, 1430, 1471, 1555, 1577,
1666, 3450. Found: C, 70.0; H, 3.6; N, 25.0%; molecular
formula C26H16N8 requires C, 70.9; H, 3.7; N, 25.4%. 1H
NMR (500 MHz, DMSO) δ (ppm): 10.74 (s, 2H), 8.00–
7.96 (m, 4H), 7.82 (t, J = 7.8 Hz, 2H), 7.80–7.76 (m, 4H),
6.85 (d, J = 7.9 Hz, 4H). 13C NMR (126 MHz, DMSO)
δ (ppm): 160.17 (s), 151.86 (s), 140.42 (s), 135.07 (s),
132.89 (s), 122.70 (s), 114.73 (s). MALDI-TOF m/z,
Da: found: 441.1, calculate for C26H17N8+: EM = 441.1
[M + H]+. ΔH°s = 191(1) kJ/mol.
(8) was synthesized following the general procedure by
interaction of 0.17 g (0.93 mmol) 4-tert-butylphthalo-
nitrile and 0.1 g (0.93 mmol) m-phenylenediamine. The
crude product was purified by column chromatography
on silica gel (benzene:acetone = 1:1) with subsequent
recrystallization from ethanol. Final drying at reduced
pressure resulted in yellow powder with yield 0.14 g, 56%
(62% [42]). Melting point: 238–240°C (235–237°,°C
[42]). UV-vis, lmax, nm (CHCl3): 334 (c = 5.73 × 10-5 M,
D = 1.23) (339 [42]). IR (KBr): n, cm-1: 688, 796, 843,
959, 1046, 1127, 1208, 1258, 1358, 1483, 1521, 1580,
1667, 2869, 2961, 3059, 3274, 3410. Found: C, 75.9; H,
6.4; N, 14.6%; molecular formula C36H34N6•H2O requires
C, 76.0; H, 6.4; N, 14.8%. 1H NMR (500 MHz, DMSO)
δ (ppm): 10.31 (s, 2H), 7.92 (d, J4 = 1.6 Hz, 2H), 7.89 (d,
J3 = 8.1 Hz, 2H), 7.80 (dd, J3 = 8.1 Hz, J4 = 1.7 Hz, 2H),
7.33 (tt, J3 = 7.8 Hz, J5 = 2.0 Hz, 2H), 6.87 (m, 2H), 6.76
(m, 4H), 1.39 (s, 18H). 13C NMR (126 MHz, DMSO) δ
(ppm): 155.75 (s), 151.86 (s), 151.53 (s), 150.14 (d, J =
4.3 Hz), 135.25 (s), 132.80 (s), 130.47 (s), 129.76 (s),
122.34 (s), 118.77 (s), 118.57 (d, J = 7.6 Hz), 113.92
(s), 35.66 (s), 31.53 (s). MALDI-TOF m/z, Da: found:
551.3, 573.3, 589.3; calculate for C36H35N6+: EM = 551.3
[M + H]+; EM = 573.3 [M + Na]+; EM = 589.2 [M + K]+.
ΔH°s = 178(4) kJ/mol.
5,26:13,18-Diimino-7,11:20,24-dimetheno-[c,n]-di
benzo-1,6,12,17-tetraazacyclodocosene-[1,3,5,7,9,12,-
14,16,21,23]-decene (6) was synthesized following the
general procedure by interaction of 0.12 g (0.93 mmol)
phthalonitrileand0.1g(0.93mmol)m-phenylenediamine.
The crude product was purified by recrystallization from
ethanol. Final drying in vacuum resulted in a yellow
product with yield 0.09 g, 45% (71% [38]). Melting
point: 379–380°C (380°C [38]). UV-vis, lmax, nm (loge),
(DMF): 327 (4.25), 340 (4.08) (328 (4.23), 343 (4.23)
[38]). IR (KBr): n, cm-1: 691, 791, 1102, 1261, 1515,
1650, 3441. Found: C, 73.2; H, 4.7; N, 18.5%; molecular
.
formula C28H18N6 H2O requires C, 73.7; H, 4.4; N,
1
18.4%. H NMR (500 MHz, DMSO) δ (ppm): 10.39 (s,
2H), 7.99–7.94 (m, 4H), 7.76–7.74 (m, 4H), 7.34 (t, J3 =
7.8Hz, 2H), 6.95 (t, J4 = 1.9 Hz, 2H), 6.78 (dd, J3 = 7.9
J4 = 2.0 Hz, 4H). 13C NMR (126 MHz, DMSO) δ (ppm):
151.63 (s), 150.10 (s), 135.21 (s), 132.36 (s), 130.48 (s),
122.52 (s), 118.64 (s), 113.97 (s). MALDI-TOF m/z,
Da: found: 439.2, 461.1, 477.1, calculate for C28H19N6+:
EM = 439.2 [M + H]+, EM = 461.1 [M + Na]+, EM =
477.1 [M + K]+. ΔH°s = 189 (3) kJ/mol.
DISCUSSION
At the first stage the influence of temperature upon the
reaction run was studied under the following experimental
conditions: fine-milled equimolecular mixtures of 1 and
4 were treated in open vessels in a focused-microwave
oven without solvent for 20 min within a temperature
range from 100°C to 200°C. It was observed that when
the temperature of the synthesis was conducted below
130°C, no macroheterocyclic system was detected in the
reaction mixtures by MALDI-TOF mass spectrometry.
When the temperature reached 150°C, the formation
of hemiporphyrazine was clearly observed. Subsequent
increases in temperature led to high molecular product
formation. Hence, corresponding hemiporphyrazines
5–8 were synthesized at 150°C for 20 min by
crossover-condensation of corresponding diamines 1
and 2 with nonsubstituted 3 and tert-butylsubstituted 4
phthalonitriles under microwave irradiation (Scheme 1).
After individual purification selected with respect
to the solubility and as described in the experimental
section, substances 5–8 were finally dried under reduced
pressure at 130°C for 4 h. Data of IR and UV-vis
spectroscopies and elemental analysis of the final
products 5–8 were found to be similar to those described
in the literature for corresponding Hps [1, 38, 41, 42] and
the characterization of these compounds was completed
with mass spectrometry data (Table 1).
2,15(16)-Di(tert-butyl)-5,26:13,18-diimino-
7,11:20,24-dinitrilo-[c,n]-dibenzo-1,6,12,17-tetra-
azacyclodocosene-[1,3,5,7,9,12,14,16,21,23]-decene
(7) was synthesized following the general procedure by
interactionof0.17g(0.93mmol)4-tert-butylphthalonitrile
and 0.1 g (0.93 mmol) 2,6-diaminopyridine. The crude
product was washed with hot hexane and purified by
column chromatography on silica gel (ethyl acetate:
hexane = 6:1). Final drying at reduce pressure resulted
in a yellow powder with yield 0.03 g, 13%. Melting
point: 276–278°C. UV-vis, lmax, nm (CHCl3): 358 (c =
4.3 × 10-5 M, D = 1.32). IR (KBr): n, cm-1: 678, 692,
800, 873, 956, 998, 1093, 1122, 1254, 1353, 1432,
1482, 1516, 1577, 1599, 1664, 2860, 2957, 3059, 3410.
Found: C, 67.4; H, 6.5; N, 18.5%; molecular formula
1
.
C34H32N8 3H2O requires C, 67.3; H, 6.3; N, 18.5%. H
NMR (300 MHz, CDCl3) δ (ppm): 8.12 (s, 2H), 8.08
(d, J4 = 1.5 Hz, 2H), 7.97 (d, J3 = 8.1 Hz, 2H), 7.76 (d,
J3 = 8.1, 2H), 7.40 (t, J3 = 7.8Hz, 2H), 6.88 (m, 4H), 1.23
(s, 18H). MALDI-TOF m/z, Da: found: 553.3, 575.3;
calculate for C34H33N8+: EM = 553.3 [M + H]+; EM =
575.3 [M + Na]+. ΔH°s = 214(5) kJ/mol.
2,15(16)-Di(tert-butyl)-5,26:13,18-diimino-
7,11:20,24-dimetheno-[c,n]-dibenzo-1,6,12,17-tetra-
azacyclodocosene-[1,3,5,7,9,12,14,16,21,23]-decene
Itisworthnotingthatnocorrespondingphthalocyanines
were detected in microwave-assisted synthesis at the
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MICROWAVE-ASSISTED SYNTHESIS AND SUBLIMATION ENTHALPIES OF HEMIPORPHYRAZINES
299
1
N
–
2
CH
–
3
–
H
4
5
N
H
6
CH
H
7
N
8
CH
X
Y
–
tBu
tBu tBu
Scheme. 1.
Table 1. Synthesis duration, yields, melting points, UV-vis and elemental analysis data of 5–8 obtained by microwave-
assisted synthesis and selected data of corresponding hemiporphyrazines synthesized in organic solvents
№
Microwave assisted synthesis (solvent-free protocol, heating at 150°C)
τsynth, min
η, %
mp, °C
l
max (loge), nm solvent
EM (without matrix), Da
Found, Da
Found, %
Calculate, %
Calculate, Da
C
N
H
5
6
7
8
20
20
20
20
29
45
13
56
346–347
379–380
276–278
238–240
352 (4.22)
DMF
441.1
441.1
C26H16N8
70.0
70.9
25.0
25.4
3.6
3.7
[M + H]+
·
327 (4.25), 340 (4.08)
DMF
439.2
439.2
[M + H]+
C28H18N6 H2O
73.2
73.7
18.5
18.4
4.7
4.4
·
358
Chloroform
553.3
553.3
[M + H]+
C34H32N8 3H2O
67.4
67.3
18.5
18.5
6.5
6.3
·
334
Hexane
551.3
551.3
[M + H]+
C36H34N6 H2O
75.9
76.0
14.6
14.8
6.4
6.4
Classical methodic (in boiling butanol)
τ
synth, min
η,%
mp, °C
l
max (loge), nm solvent
Lit.
[1]
354 (4.31)
DMF
5
6
7
8
480
38
344
328 (4.23), 343 (4.23)
DMF
1020
900
71
60
62
380
—
[38]
[41]
[42]
373
EtOH
333
Hexane
720
235–237
temperature equal to 150°C based on both nonsubstituted
3 and tert-butylsubstituted 4 phthalonitriles. This fact
can be explained by an initial attack of amino group of
diamine toward carbon atom of one of the cyano groups
of phthalonitrile which is transformed into dimer 9b
via intermediate 9a (Scheme 2). The dimerization of
two-unit intermediate 9b leads to the hemiporphyrazine
macrocycle. (The) A similar mechanism was described in
the literature [14, 43, 44].
Microwave irradiation in the Hps synthesis illustrated
two improvements. First, the time of the synthesis was
reduced drastically from 8–10 h to 20 min. The second
Copyright © 2019 World Scientific Publishing Company
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300
A. S. KUZNETSOVA ET AL.
Scheme. 2.
(a)
(b)
(c)
(d)
Fig. 1. MALDI-TOF mass spectra without matrix of 5 (a), 6 (b), 7 (c) and 8 (d)
improvement involved the elimination of a solvent during
the synthesis.
It was earlier established that hemiporphyrazines can
be sublimated under vacuum [1, 32], but thermodynamic
characteristics of these processes have not been reported
yet. The mass spectrometric studies performed in the
connection with a sublimation process show that 5–8 give
stable streams of particles at a range of temperatures T =
441–531 K. In all four cases the dependences ln(I.T) =
f(1000/T) (Fig. 2) were found to be close to straight lines
(the correlation coefficient was 0.999 in all four cases),
which is usually observed for the vaporization in the
present temperature range without changes of aggregate
state of solid phase.
In the case of 1 a large number of byproducts (starting
materials, intermediates and various products of condensa-
tion) along with Hps 5 and 7 were detected by MALDI-TOF
of the reaction mass. The usage of m-phenylenediamine 2
led to obtaining of 6 and 8 with moderate yields.
Along with the main signals which correspond to
[M + H]+ ions, the signals of [M + Na]+ and [M + K]+ ions
were detected in MALDI-TOF (Fig. 1). Good conformity
between the calculated isotopic distributions and those
derived from experimental data proves this assignment.
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MICROWAVE-ASSISTED SYNTHESIS AND SUBLIMATION ENTHALPIES OF HEMIPORPHYRAZINES
301
14
13
12
11
10
9
14
13
12
)
T
)
I
(
T
I
n
l
(
11
10
9
n
l
N
N
N
N
N
NH
HN
NH
HN
N
N
N
N
N
8
8
7
1.85
1.90
1.95
2.00
2.05
2.10
2.15
1.90
1.95
2.00
2.05
2.10
2.15
2.20
10 3/T, K -1
10 3/T, K -1
12
11
10
9
12
11
10
9
)
T
I
(
)
T
n
l
I
(
n
l
N
N
N
N
N
N
NH
HN
NH
HN
8
8
N
N
N
N
7
7
1.95
2.00
10 3/T, K -1
2.05
2.10
2.05
2.10
2.15
10 3/T, K -1
2.20
2.25
2.30
Fig. 2. Dependence of the molecular ion intensity logarithm of 5–8 on temperature
Table 2. Values of sublimation enthalpies for investigated compounds 5–8
Compound
5
6
7
8
ΔH°s, kJ/mol
191 (1)*
189 (3)
214 (5)
178 (4)
*Parenthesized values are estimated errors calculated as 3σLS
.
One can see that hysteresis items are practically
absent at temperature increase and decrease. This allows
for consideration that the points in the plots correspond
to the equilibrium states. The enthalpy of sublimation
values ΔHs for compounds 5–8 were calculated by linear
regression using the Clausius–Clayperon equation and
collected in Table 2.
Although the experimental data were not recorded in a
broad temperature range, it is considered that the enthalpy
of sublimation does not depend on the temperature range
under study (ΔCp = 0).
irradiation was applied to the synthesis of hemi-
porphyrazines (5–8). It was established that the reactions
ran under solvent-free protocol with essential reduction
in synthesis duration from 8–12 h to 20 min. Based on
mass spectrometric investigations, it was established that
hemiporphyrazines 5–8 form a stable stream of particles
and their enthalpies of sublimation were estimated using
the Clausius–Clayperon equation.
Acknowledgments
The part of this work devoted to synthesis is supported
by the Russian Foundation for Basic Research under
grant № 19-03-00888.
The part of this work devoted to determination
of enthalpy of sublimation by mass spectrometric
investigations is supported by the Russian Science
Foundation under grant № 17-73-10198.
CONCLUSION
A new approach consisting of initialization of 2,6-dia-
minopyridine or 1,3-phenylenediamine with phthalonit-
rile or 4-tert-butylphthalonitrile reactions by microwave
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A. S. KUZNETSOVA ET AL.
Some of the research was performed using the
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