Convenient One-Step Synthesis of Benzotriazolylsuccinimides in Melt

Article abstract of DOI:10.1002/jhet.2557

The one-step interaction of 1H-benzotriazoles with maleimides in melt at elevated temperatures has resulted in benzotriazolylsuccinimides. According to spectroscopy data, benzotriazolylsuccinimides obtained contain both major (benzotriazol-1-yl)-succinimide residue and minor (benzotriazol-2-yl)-succinimide residue. An effect of substituents in the initial reagents on the fine splitting of carbon peaks in ¹³C NMR spectrums of benzotriazolylsuccinimides is discussed. The influence of structure of benzotriazolylsuccinimides on their crystallinity degree is also discussed.

Full text of DOI:10.1002/jhet.2557

Month 2015
Convenient One-Step Synthesis of Benzotriazolylsuccinimides in Melt
a
a,b
Ivan. A. Farion, Dmitrii M. Mognonov, Vitaliy F. Burdukovskii,a,b Bato Ch. Kholkhoev,a,b and Petr S. Timashevc
*
aBaikal Institute for Nature Management, Siberian Branch of Russian Academy of Sciences, Sakhyanovoy Street, 6,
Ulan-Ude, 670047, Russia
bBuryat State University, Smolina Street, 24a, Ulan-Ude, 670000, Russia
cInstitute of Laser and Information Technologies, Russian Academy of Sciences
Pionerskaya Street, 2, Troitsk, Moscow, Russia
*
E-mail: fariv@mail.ru
Received May 22, 2015
DOI 10.1002/jhet.2557
Published online 00 Month 2015 in Wiley Online Library (wileyonlinelibrary.com).
The one-step interaction of 1H-benzotriazoles with maleimides in melt at elevated temperatures has re-
sulted in benzotriazolylsuccinimides. According to spectroscopy data, benzotriazolylsuccinimides obtained
contain both major (benzotriazol-1-yl)-succinimide residue and minor (benzotriazol-2-yl)-succinimide resi-
due. An effect of substituents in the initial reagents on the fine splitting of carbon peaks in 13C NMR spec-
trums of benzotriazolylsuccinimides is discussed. The influence of structure of benzotriazolylsuccinimides
on their crystallinity degree is also discussed.
J. Heterocyclic Chem., 00, 00 (2015).
INTRODUCTION
N-methylmaleimide was interacted with bis(benzotriazole-1-
ylmethyl)hydroxylamine in toluene medium for 24 h and with-
out trifluoroacetic acid. Flammable (toluene), irritant, and
highly corrosive (trifluoroacetic acid) liquids were used in the
both cases. Bisderivatives of 1H-benzotriazole, where one
1,2,3-benzotriazole unit was only consumed in reaction, were
also utilized. In addition to this, a long period of time of reac-
tion was required. We have offered the one-step synthesis of
benzotriazolylsuccinimides in melt by means of the convenient
reaction of the nucleophilic Michael addition of 1H-
benzotriazoles to maleinimides. The absence of toxic, flamma-
ble, and corrosive solvents, catalysts as well as a lack of
by-products evolution are the advantages of such reaction in
terms of the green chemistry and the atom efficiency. To the
best of our knowledge, information about such melt reaction
between 1H-benzotriazoles and maleimides in the scientific
literature is absent, excepting the works of the authors of the
presented article and other authors [16] who referenced to
our previous work [17]. This article is devoted to the continu-
ation of our work concerning the melt synthesis and the inves-
tigation of benzotriazolylsuccinimides.
1H-Benzotriazole is known to be one of interesting
aromatic heterocyclic condensed compounds. In practice,
1H-benzotriazole is used as the antifogging agent in the pho-
tography and the corrosion inhibitor [1–3] as well as for pro-
moting the urea nitrification process in soil [4]. For
derivatives of 1H-benzotriazole, 2-aryl-substituted 1,2,3-
benzotriazoles are utilized as the UV-stabilizers of polymers
[5]. Polymers containing 2-aryl-substituted 1,2,3-
benzotriazole units within a macromolecule are used in the
elctrochromic devices [6]. 1H-Benzotriazole possesses high
N-H acidity (pKa 8.2 in water [7]), and the excellent ability
to form complex coordination compounds [8–10].
1H-benzotriazole and its derivatives take part in such reac-
tions as N2 abstracting followed by the cyclization [11]; the nu-
cleophilic substitution [12–14] and the Michael nucleophilic
addition to the electron-deficient π-bonds [7]. For information
about the nucleophilic Michael addition of derivatives of 1H-
benzotriazole to the maleinimide olefinic bond, there is an ex-
ample of reaction of N-methylmaleimide with (benzotriazol-1-
yl)methylene((benzotriazol-1-yl)methyl)amine under heating
in toluene medium for 48 h and in the presence of
trifluoroacetic acid. Such reaction has resulted in N-methyl-
3-(1-benzotriazolyl)-pyrrolidin-2,5-dione formation [15].
Besides, N-methyl-3-(1-benzotriazolyl)-pyrrolidin-2,5-dione
together with N-methyl-3-(2-benzotriazolyl)-pyrrolidin-2,5-
dione were obtained by those authors as by-products when
RESULTS AND DISCUSSION
Syntheses and NMR investigations of benzotriazolylsuccinimides.
1-(2,5-Dioxo-1-phenylpyrrolidin-3-yl)-benzotriazole 1 and bis[3-
(benzotriazolyl)succinimides] 2a-c. Previously [17], we carried
© 2015 HeteroCorporation

I. A. Farion, D. M. Mognonov, V. F. Burdukovskii, B. Ch. Kholkhoev, and P. S. Timashev
Vol 00
out the melt one-step condensation of 1H-benzotriazole with N-
phenylmaleimide as well as bismaleimides with 2mol of 1H-
benzotriazole in a fluoroplast reactor according to reactions 1
and 2 (Scheme 1), respectively. Purified 2a–c, in contrast to
crystalline 1, are white amorphous powders and cannot be
crystallized. If compared the 13C NMR spectrum data of 1
with the ones of 2b, which are summarized in Table 1, the
peaks of the minor (benzotriazol-2-yl)-succinimide residue
appear in the 13C NMR spectrum of 2b as the ones of the
smaller intensity at δ 36.27, 63.71, 118.20, 127.51, 144.21,
171.40, and 173.24ppm. The similar peaks of the minor
(benzotriazol-2-yl)-succinimide residues appear also in the 13C
NMR spectra of 2a and 2c. For 1a, this compound was
investigated by authors [16] who observed the 13C NMR
peaks of 1a that are similar to the 13C NMR ones of the minor
(benzotriazol-2-yl)-succinimide residues of 2b-c. The ratios of
an integral intensity of the C(3′)H and C(3‴)H protons in the
1H NMR spectrums of 2a–c were ascertained to be 7.0 (for
2a), 4.5 (for 2b), and 7.0 (for 2c), proving additionally the
lesser content of the (benzotriazol-2-yl)-succinimide residues.
Thus, the NMR investigations of 1 and 2a–c, along with a
comparison with the NMR data of 1a [16], have revealed that
1H-benzotriazoles interact with maleimides in melt at high
temperatures to afford benzotriazolylsuccinimides comprising
both major (benzotriazol-1-yl)-succinimide residue and minor
(benzotriazol-2-yl)-succinimide residue.
Scheme 1. Synthesis of benzotriazolylsuccinimides in melt (1 and 2a–c were synthesized by us previously [17]).
Table 1
Characteristics of benzotriazolylsuccinimides.
13С NMR chemical shifts of succinimide carbons (DMSO-d6), ppma
Compound
C(2′)
172.33
173.13
172.31
171.59
172.26
172.32
C(2‴)
C(5′)
173.19
174.22
173.19
172.42
173.13
173.15
C(5‴)
C(3′)
C(3‴)
C(4′)
C(4‴)
Yieldb (%)
CDc (%)
1
–
–
56.34
55.80
56.28
55.72
56.23
56.37
55.94
56.01
56.52
56.60
–
35.43
35.33
35.40
35.13
35.35
35.37
35.28
35.31
35.25
35.28
–
71
85
88
91
75
–
72
–
68
–
59d
–
2a
2b
2c
3a
172.20
171.40
170.66
171.39
–
171.25
–
170.74
–
174.28
173.24
172.55
173.22
–
173.21
–
173.08
–
63.40
63.71
63.20
63.61
–
63.56
–
64.31
–
36.16
36.27
36.01
36.25
–
36.20
–
36.32
–
5e
–
6e
–
3b
3c
Seven peaks at
172.06–172.15
171.80
Eight peaks at
172.93–173.08
172.87
5.5e
–
10e
–
171.95
172.92
aCarbon indexes correspond to ones on Scheme 1.
bPurified compounds.
cCD is crystallinity degree that has been calculated as the ratio of an amorphous area to a total (amorphous + crystalline) one on the X-ray powder
diffractograms.
dmp 145–147°C.
eAmorphous.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2015
Convenient One-Step Synthesis of Benzotriazolylsuccinimides in Melt
bis[(N-phenylsuccinimid-3-yl)benzotriazoles] 3a–c.
Next,
Crystallinity degree of bezotriazolylsuccinimides.
A
it was interesting to carry out the syntheses of
benzotriazolylsuccinimides via the interaction of 5,5′-
bisbenzotriazoles with 2 mol of N-phenylmaleimide. 5,5′-
Bisbenzotriazoles contain, in contrast to 1H-benzotriazole, the
two nonequivalent 1-nitrogen atoms because of bridge groups
located between the benzene rings. In more detail, 5,5′-
bisbenzotriazoles possess all the three nonequivalent nitrogen
atoms in each 1H-benzotriazole residue that must contribute
to specific NMR spectral patterns and other properties of
reaction products. Hence, as the continuation of our work, we
have realized the syntheses of methylene-3a, oxa-3b, and
dioxothia-3c bis[(N-phenylsuccinimid-3-yl)-benzotriazoles]
via the condensation of 5,5′-bisbenzotriazoles such as 5,5′-
bisbenzotriazol methane, 5,5′-bisbenzotriazol oxide, and 5,5′-
bisbenzotriazol sulfone with 2 mol of N-phenylmaleimide
according to reaction 3 (Scheme 1). Purified 3a–c are white
amorphous powders and cannot be crystallized. The values of
the 13C NMR resonance peaks of the succinimide carbons of
3a-c are summarized in Table 1. The intensive resonances
of the carbonyl, methine, and methylene succinimide carbons
of 3a that correspond to the carbons of the major
(benzotriazol-1-yl)-succinimide residue are split onto the two
peaks. This fact may be explained in terms of nonequivalence
of the 1-nitrogen atoms in the bisbenzotriazolyl residues of 3a
because of the bridge group of CH2 located between the
benzene cycles. The similar situation is observed for
compound 3c with the sulfone bridge group. Signals for the
carbons of the (benzotriazol-2-yl)-succinimide residues in
the 13C NMR spectrums of 3a–c are not split. This is due to
the symmetrical character of the benzotriazol-2-yl residue.
The resonance peaks for the carbonyl and methine carbons of
the succinimide cycle of the (benzotriazol-1-yl)-succinimide
residues of 3c are split analogously to the similar carbons of
3a. The peaks of the carbonyl carbons of the nonsymmetrical
(benzotriazol-1-yl)-succinimide residues of 3b are split on
seven and eight peaks. That is, they are split to the greater
extent than the analogous peaks of 3a and 3c. This
phenomenon appears to be due to the different electronic
influences of the oxygen (the electron donor), methylene (the
very weak electron donor because of absense of a lone pair of
electrons) and sulfone (the electron acceptor) bridge groups
on the benzotriazolyl nitrogens. The π-donating properties of
the lone pair of electrons of the bridge oxygen in 3b appear to
be influenced by a metha-position or para-position of the
N¼N electron-acceptor group in the benzotriazol-1-yl
residues or two C¼N electron-acceptor groups in the
benzotriazol-2-yl residue. Hence, a mutual π-electronic
influence of one benzotriazolylsuccinimide residue on another
benzotriazolylsuccinimide residue, which is transmitted via
the bridge oxygen, should take place. Such mutual influence
may be the cause of the fine splitting of the 13C NMR signals
of the carbonyl succinimide carbons of the nonsymmetrical
(benzotriazol-1-yl)-succinimide residues in 3b.
crystallinity degree of bezotriazolylsuccinimides is presented
in Table 1. 1 possesses the higher value of this parameter of
59%, probably because of the single isomer presence. For
other compounds 2b and 3a–c, a value of the crystallinity
degree varies from 5 to 10 %, evidencing their amorphness.
Amorphous nature of these compounds appears to be due to
the presence of the six probable isomers of a benzotriazol-1-yl
residue and (or) benzotriazol-2-yl residue position with
respect to bissuccinimide (Scheme 2) bridge groups or a
N-phenylsuccinimid-3-yl residue position with respect to
a bridge group (ꢀXꢀ) located between the benzene rings of
the bisbenzotriazolyl fragments (Scheme 3). In addition,
every position isomer contains the two asymmetrical
succinimide carbons, rendering possible the presence of the
DD-stereoisomer, LL-stereoisomer, and DL-stereoisomer in
one of position isomers. All this hinders the packing of
molecules onto crystalline structure and favors the formation
of amorphous powders.
Proposed reaction mechanism of benzotriazolylsuccinimides
formation.
The proposed reaction mechanism of the
benzotriazolylsuccinimides formation is presented on the
Scheme 4. Reaction begins with the nucleophilic attack of
the lone pair of electrons of the sp2-hybridized “pyridine”
Scheme 2. Probable isomers of the benzotriazol-1-yl residue and (or)
benzotriazol-2-yl residue position with respect to the bissuccinimide
bridge groups.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

I. A. Farion, D. M. Mognonov, V. F. Burdukovskii, B. Ch. Kholkhoev, and P. S. Timashev
Vol 00
Scheme 3. Probable isomers of the N-phenylsuccinimid-3-yl residue po-
sition with respect to bridge groups located between the benzene rings of
the bisbenzotriazolyl groups.
Scheme 4. The proposed reaction mechanism of benzotriazolylsuccinimides
formation.
nitrogens of 1H-benzotriazole on the electron-deficient
C¼C bond of maleimides followed by the charged
intermediates formation. These charged intermediates are
transformed to the “enolic” neutral intermediates across a
proton transfer. After, the enolic neutral intermediates are
isomerized into benzotriazol-1-yl-succinimides or benzotriazol-
2-yl-succinimides. The benzotriazol-2-yl residue contains the
ortho-benzoquinoid fragment that is energetically less
favorable than the benzoid fragment of the benzotriazol-1-yl
residue. This fact explains the higher content of the
nonsymmetrical benzotriazol-1-yl residues in reaction
products.
The amorphous character of bisbenzotriazolylsuccinimides
has been proved to be the consequence of the presence of the
six probable isomers of a position of N-phenylsuccinimid-3-yl
or benzotriazol-1-yl residue and (or) benzotriazol-2-yl residue
with regard to the bridge groups in the bisbenzotriazolyl or
bissiccinimidyl residues, respectively. The additional cause
of the amorphous character of such compounds may be that
every position isomer contains the two asymmetrical
succinimide carbons, rendering possible the presence of the
DD-stereoisomer, LL-stereoisomer, and DL-stereoisomer in
one of position isomers.
CONCLUSIONS
1H-Benzotriazoles react with maleimides in melt via ad-
dition to the double bond of the latter to afford both major
(benzotriazol-1-yl)succinimide and minor (benzotriazol-2-
yl)succinimide. For the products of an interaction of 5,5′-
bisbenzotriazoles with 2mol of N-phenylmaleimide, they
contain two kinds of the nonsymmetrical (benzotriazol-1-
yl)-succinimide residues and single kind of the symmetrical
(benzotriazol-2-yl)-succinimide residues. These results are
evidence that all the three nitrogen atoms of benzotriazoles
participate in the nucleophilic addition to maleimides.
EXPERIMENTAL
Fourier transform ir spectra were recorded with a
“IFS25” instrument in KBr tablets. 13C and 1H NMR
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2015
Convenient One-Step Synthesis of Benzotriazolylsuccinimides in Melt
spectra were obtained on a Varian VXR-500S spectrometer
at 126.7 and 500 MHz, respectively, in DMSO-d6 and
CDCl3; the signals of the residual protons for DMSO-d6
NH). ir: CH2 1400, 3070, 2950, NH 3333–3400 cmꢀ1. Anal.
Calcd for C13H10N6: C, 62.39; H, 4.03; N, 33.58. Found: C,
62.15; H, 3.90; N, 33.16.
1
(δ= 2.5ppm), CDCl3 (δ = 7.24ppm) in H NMR spectra
5,5′-Bisbenzotriazol oxide was synthesized similar to
5,5′-bisbenzotriazol methane, with the charge of 3,3′,4,4′-
tetraaminodiphenyl ether being 22.2 g (0.0964 mol).
and for the carbon atoms of DMSO (δ = 39.7ppm) in 13C
NMR spectra served as the internal standard. Melting
points were determined on a “IA9100” instrument and
not corrected. X-ray powder diffractograms were run on a
“D8 ADVANCE” diffractometer of “Brucker ACX,”
Germany. The conditions of the diffractograms runs were
CuKα-radiation and a “Vantec-1” detector.
1
15.72 g (82%), mp 263–264°C. H NMR (DMSO-d6), δ
7.34–7.42 (d, J= 19.5 Hz, 2H, phenyl protons), 7.78 (s,
2H, phenyl protons), 7.81–7.89 (d, J= 19.5Hz, 2H, phenyl
protons), 15.54 ppm (br s, 2H, NH). ir: NH 3325–3410,
ꢀO– 1247cmꢀ1. Anal. Calcd for C12H8N6O: C, 57.14;
H, 3.20; N, 33.32. Found: C, 57.03; H, 3.28; N, 33.12.
Ice CH3COOH, HCOOH, NaHSO3, NaNO2, and NaOH of
the chemical pure grade were used as received. N-
phenylmaleimide was prepared according to the method cited
in the article [18]. All the solvents applied were purified ac-
cording to the known procedures [19]. 1H-Benzotriazole
was crystallized from benzene, mp 98–99°C. Bismaleimides
were synthesized similar to the procedures [20].
3,3′,4,4′-tetraaminodiphenyl methane was purified by
refluxing in distilled water in the presence of NaHSO3 and char-
coal. After a hot filtration and cooling, precipitated crystals were
filtered off and rinsed with distilled water and dried in vacuo at
40–50°C, mp 140–142°C. 3,3′,4,4′-Tetraaminodiphenyl ether
was purified as 3,3′,4,4′-tetraaminodiphenyl methane, mp
150–151°C. 3,3′,4,4′-Tetraaminodiphenyl sulfone was purified
as 3,3′,4,4′-tetraaminodiphenyl methane and 3,3′,4,4′-
tetraaminodiphenyl ether, mp 173–174°C.
5,5′-Bisbenzotriazol sulfone.
The synthesis must be
carried out in a fume chamber because of an evolution of
nitrous oxides. 3,3′,4,4′-Tetraaminodiphenyl sulfone (10g,
0.0336 mol) and ice CH3COOH (85 mL) were placed into a
1.5L three-neck flask equipped with a stirrer, an inlet and an
outlet of argon, and a thermometer. Flask content was
heated up to 50°C under stirring until the complete
dissolution of solids. Then, at 50°C, solution of NaNO2 (7g,
0.102 mol) in distilled water (20 mL) was quickly added to
the flask content intensively stirred. After addition of
NaNO2 solution, reaction masse boils up sharply (“Careful!
Eye protectors and protective gloves must be used!”)
The content was gradually cooled to room temperature,
with a suspension precipitating throughout this period.
Then the suspension was filtered off and rinsed with dis-
tilled water several times and dried in vacuo at 50–60°C.
Crude 5,5′-bisbenzotriazol sulfone was dissolved in
HCOOH under heating and refluxed in the presence of
charcoal. After a hot filtration, filter liquor was cooled
gradually to room temperature. Fine crystals were filtered
off and rinsed with HCOOH. The operation of the
purification was carried out once again. After purification,
5,5′-bisbenzotriazol sulfone was dried in vacuo at 70–80°C.
8.42 g (85%), mp 292–294°C. 13C NMR (DMSO-d6)
δ 115.18, 118.00, 124.2, 132.66, 135.72, 140.22 ppm
(aromatic carbons). Anal. Calcd for C12H7N6O2S: C,
48.00; H, 2.69; N, 27.99. Found: C, 47.88; H, 2.78; N,
27.82.
5,5′-Bisbenzotriazol methane.
The synthesis must be
carried out in a fume chamber because of an evolution of
nitrous oxides. A 0.5L three-neck flask equipped with a
stirrer, an inlet and an outlet of argon, and a thermometer was
charged with mixture of ice CH3COOH (110 mL) and
distilled water (55mL), and then 3,3′,4,4′-tetraaminodiphenyl
methane (22g, 0.0964 mol) was added. Flask content was
heated under stirring until complete dissolution of solids.
Solution was cooled to 13–14°C, and then the cooling bath
was removed. After that, solution of NaNO2 (18 g, 0.261 mol)
in distilled water (40mL) was quickly added to the flask
content under stirring. Temperature of flask content rose up to
60–70°C. The content was stirred for about 1 h, with a
suspension precipitating throughout this period. The
suspension was poured into cold distilled water (500–600mL)
and stirred. The product was filtered off and rinsed with
distilled water and dried in vacuo at 50–60°C. Crude 5,5′-
bisbenzotriazol methane was dissolved in ice CH3COOH
under heating and refluxed in the presence of small quantities
of distilled water and charcoal. After a hot filtration, filter
liquor was poured into cold distilled water (500–600mL) and
stirred. Precipitated 5,5′-bisbenzotriazol methane was filtered
off, rinsed several times with distilled water, and dried in
1-(2,5-dioxo-1-phenylpyrrolidin-3-yl)-benzotriazole 1. 1H-
Benzotriazole
(1.1913 g,
0.01 mol)
and
N-
phenylmaleimide (1.7937 g, 0.01mol) were carefully
mixed and put in a fluoroplast reactor. Then the reactor
was placed into a bath heated up to 120°C. Temperature
of the bath was risen up to 220°C. Reaction mixture was
held at 220°C for 5 min, then cooled to ambient
temperature, and removed from the reactor. The product
was dissolved in a mixture of HCOOH and H2O,
refluxed for 10min in the presence of activated charcoal,
then filtered off. The pH of mother solution was adjusted
to about 5 with 0.5% aqueous NaOH. Precipitate was
filtered off, dissolved in boiling ethanol, and gradually
cooled. The fine crystals were filtered off and dried
1
vacuo at 70–80°C. 19.02 g (85%), mp 240–241°C; H NMR
(DMSO-d6), δ 4.29 (s, 2H, CH2), 7.34–7.42 (d, J= 19.5 Hz,
2H, phenyl protons), 7.78 (s, 2H, phenyl protons), 7.81–7.89
(d, J=19.5 Hz, 2H, phenyl protons), 15.46 ppm (br s, 2H,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

I. A. Farion, D. M. Mognonov, V. F. Burdukovskii, B. Ch. Kholkhoev, and P. S. Timashev
Vol 00
in vacuo at 50–70°C. 2.12g (71%), mp 145–147°C. ir: CO
1717.5, C–N–C 1187.5, CH2 and CH 2930, 2979cmꢀ1
H, 3.70. Found: C, 64.45; H, 3.68. Compound 3c. 2.20 g
(68%). Anal. Calcd for C32H22N8O6S: C, 59.44; H, 3.43.
.
Anal. Calcd for C16H12N4O2: C, 65.74; H, 4.14; N,
19.17. Found: C, 65.90; H, 4.15; N, 18.98. 13C NMR
peaks are shown in Table 1.
Found: C, 59.62; H, 3.42.
Acknowledgments. The authors thank Alexey K. Subanakov
and Roman V. Kurbatov from the Laboratory of Oxide
Systems of the Baikal Institute for Nature Management SB
RAS for the runs of the X-ray powder diffractograms and
the interpretation of them. This work is supported by the
Russian Foundation for Basic Research, grant no. 14-29-10169
ofi_m (benzotriazolylsuccinimides synthesis) and Russian
Science Foundation, grant no. 14-13-01422 (NMR spectral
studies).
General procedure for synthesis of bis[3-(benzotriazolyl)
succinimides]
2a–c.
1H-Benzotriazole (2.3826g,
0.02mol) and either N,N′-hexamethylene–bismaleinimide
(2.7629 g, 0.01mol) (for 2a), or 4,4′-diphenylmethane–
bismaleinimide (3.5835 g, 0.01mol) (for 2b), or 4,4′-
bis(maleimido)-diphenyl ether (3.6032g, 0.01mol) (for
2c) were placed in a fluoroplast reactor. Reaction was
carried out as described in the preceding text for 1.
Purification of 2a-c was also carried out as described for
1. The products were precipitated as amorphous powders
after purification, then filtered off, and dried in vacuo at
50–70°C. 13C NMR peaks of 2a–c are shown in Table 1.
2a. 4.37 g (85%). ir: CO 1714, CH2 and CH 2941, 2860,
ortho-phenylene 746 cmꢀ1. Anal. Calcd for C26H26N8O4:
C, 60.69; H, 5.09. Found: C, 60.49; H, 4.98. 2b. 5.25g
(88%). ir: CO 1721, 1731, CH2, and CH 2944, 2854,
ortho-phenylene 746, C–N–C 1386 cmꢀ1. Anal. Calcd for
C33H24N8O4: C, 66.44; H, 4.05. Found: C, 66.53; H,
4.13. 2c. 5.45 g (91%). ir: CO 1715, 1732, ꢀO– 1242,
ortho-phenylene 746, C–N–C 1393 cmꢀ1. Anal. Calcd for
C32H22N8O5: C, 64.21; H, 3.70. Found: C, 64.46; H, 3.74.
General procedure for synthesis of bis[(N-phenylsuccinimid-
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A fluoroplast reactor was
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charged with 5,5′-bisbenzotriazol methane (for 3a)
(1.2513g, 0.005mol) and either 5,5′-bisbenzotriazol oxide
(for 3b) (1.2612g, 0.005mol) or 5,5′-bisbenzotriazol
sulfone (for 3c) (1.5015g, 0.005mol), and N-
phenylmalrimide (1.7317g, 0.01mol) were placed in a
fluoroplast reactor. Reaction was carried out as described
in the preceding text for 1. Purification of 3a-c was also
carried out as described for 1. The products were
precipitated as amorphous powders after purification, then
filtered off, and dried in vacuo at 50–70°C. 13C NMR
peaks of 3a–c are shown in Table 1.
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Compound 3a. 2.24g (75%). ir: CO 1724, 1795, CH2
and CH 2787–3062 cmꢀ1. Anal. Calcd for C33H24N8O4:
C, 66.44; H, 4.05. Found: C, 66.68; H, 4.13. Compound
3b. 2.15 g (72%). Anal. Calcd for C32H22N8O5: C, 64.21;
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet