Rational design of an efficient one-pot synthesis of 6H-pyrrolo[2,3,4- gh] perimidines in polyphosphoric acid

Article abstract of DOI:10.1039/c6ra17269e

Several highly efficient one-pot synthetic protocols were developed, enabling polyphosphoric acid-activated nitroalkanes to act as electrophiles in reactions with aminonapthalenes. The featured methods allow for the single step assembly of polyheterocycli

Full text of DOI:10.1039/c6ra17269e

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DOI: 10.1039/C6RA17269E.
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ARTICLE
Rational Design of an Efficient One-Pot Synthesis of 6H-
pyrrolo[2,3,4-gh]perimidines in Polyphosphoric Acid†
Received 00th January 20xx,
Accepted 00th January 20xx
Alexander V. Aksenov,*a Nicolai A. Aksenov,a,b Dmitrii S. Ovcharov,a Dmitrii A. Aksenov,a
Georgii Griaznov,a Leonid G. Voskressensky,b and Michael Rubin*a,c
DOI: 10.1039/x0xx00000x
Several highly efficient one-pot synthetic protocols were developed, enabling polyphosphoric acid-activated nitroalkanes
to act as electrophiles in reactions with aminonapthalenes. The featured methods allow for the single step assembly of
polyheterocyclic aromatic derivatives of 6H-pyrrolo[2,3,4-gh]perimidine scaffold in high yields.
www.rsc.org/
Introduction
N
N
N
N
1H-Cyclopenta[cd]phenalenes
2 are interesting polycyclic
aromatic architectures that can be viewed as derivatives of the
acenaphthene system peri-anneleated by a benzene ring.
These compounds attract the attention of chemists and
material scientists due to being the smallest structural units
modeling orbital and physico-chemical properties of fullerenes
and defected carbon nanotubes.1 Along with pyrene (1)
derivatives, such compounds could be used as fluorescent
probes and light-sensing units in various biochemical assays.2
However, due to a very low solubility in water and significant
carcinogenicity, the potential of these structural fragments for
cytological and in vivo applications could be limited. We
pondered if this issue can be addressed by partial replacement
of carbon with nitrogen atoms3 to afford aromatic polyhetero-
cyclic scaffolds with improved solubility, which also are
expected to show much lower metabolitic stability. We
previously demonstrated several synthetic approaches
towards 1,3-diazopyrenes 3, which we intended as a conveni-
ent substitute of the pyrene unit for material science
applications.45 We also invested efforts in the development of
synthetic approaches towards 6H-pyrrolo[2,3,4-gh]perimidine
scaffold 4, primarily capitalizing on peri-annulations of a
pyrrole ring to 1H-perimidines (Figure 1).6 Furthermore, we
recently reported on umpolung-activation of nitroalkanes 6
toward the addition of carbon- and nitrogen-based nucle-
ophiles with polyphosphoric acids (Scheme 1). This chemistry
was employed for the installation of amino and carboxamide
groups via direct C-H functionalization of arenes 5 (Scheme 1,
eq. 1)7 and for efficient preparation of benzoxazoles and benz-
HN
1
2
3
4
Figure 1.
RCH2NO2 (6)
(1)
H
NHCOR
PPA
7
5
Me2CHNO2
PPA
N
H
8
NH2
XH
R
RCH2NO2 (6)
(2)
OPO(OH)2
PPA
N
H
N
H
XH
9
10
N
X
R
X = O, NH
11
Scheme 1
imidazoles 11 (Scheme 1, eq. 2).8 Herein we wish to report our
synthetic studies towards 6H-pyrrolo[2,3,4-gh]perimidine 4
employing this unusual chemistry.
Results and discussion
Polyphosphoric acid (PPA) possesses an array of unique
physico-chemical properties, which makes it a very attractive
ionic liquid-like reaction medium to carry out cascade and one-
pot transformations involving acid-catalyzed steps, such as
electrophilic aromatic substitution, Schmidt and Beckmann
rearrangements, Vilsmeier-type reactions, nucleophilic substit-
utions, as well as various acid-promoted elimination and
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DOI: 10.1039/C6RA17269E
OPO(OH)2
NH2
NH2
H
N
R
N
6a: R1 = H; 6b: R1 = Me;
6c: R1 = Ph; 6d: R1 = CH2Ph
6e: R1 = n-C5H11
6f: R1 = 3-C6H4Cl;
6g: R1 = 4-C6H4OMe;
6h: R1 = 4-C6H4Cl;
OPO(OH)2
H
OPO(OH)2
NH2
N
12
;
R
OPO(OH)2
PPA, H
-H3PO4
PPA
R1
12
N
R1CH2NO2
H2N
H2N
6
19
OPO(OH)2
20
H
N
NH2
H
N
H
N
NH2 OPO(OH)2
2 R
R
N
OPO(OH)2
OPO(OH)2
N
12
N
NH
N
R1
- NH2OPO3H2
- H
PPA
R2
N
H
R2
N
H
13a: R = H;
13b: R = Me
H2N
H2N
14
21
13
13a: R2 = H;
13b: R2 = Me;
13c: R2 = Ph
NH
OPO(OH)2
NH
OPO(OH)2
NH2
R
NH2
NH
R1
N
-H3PO4
18aa: R = H, 61%
18bb: R = Me, 67%
N
N
R1
R
N
+ H
R2
N
H
R2
N
H
Scheme 3
15
16
NH
R1
NH
(6d), and 1-nitrohexane (6e), were also employed in the
reaction with 6-amino-1H-perimidines 13b,c substituted at C-2
to afford the corresponding 6H-pyrrolo[2,3,4-gh]perimidines
with different substituents C-2 and C-7 (Scheme 2).
Remarkably, these compounds were obtained as sole products
and isolated in pure form after aqueous work up followed by
recrystallization. Purification by column chromatography was
not required.
R1
N
- NH2OPO3H2
-H3PO4
N
R2
N
H
17
R2
N
18
OPO3H2
18aa: R1 = R2 = H (58%);
18da: R1 = CH2Ph, R2 = H (62%);
18ab: R1 = H, R2 = Me (62%);
18ac: R1 = H, R2 = Ph (67%);
18ba: R1 = Me, R2 = H (61%);
18bb: R1 = R2 = Me (68%);
18bc: R1 = Me, R2 = Ph (71%);
18ca: R1 = Ph, R2 = H (54%);
18db: R1 = CH2Ph, R2 = Me (67%);
18dc: R1 = CH2Ph, R2 = Ph (66%);
18ea: R1 = n-C5H11, R2 = H (56%);
18fb: R1 = 3-C6H4Cl, R2 = Me (63%);
Next, we decided to investigate the possibility of gener-
ating 6-amino-1H-perimidines species 13 in situ. It was
anticipated that generation of phosphorylated aci-form 12 in
the presence of naphthalene-1,4,5-triamine (19) would induce
nucleophilic attack by one of the amino-groups affording
phosphorylated iminamide 20 (shown in protonated from in
Scheme 3). The later would undergo a 6-exo-trig cyclization
involving a second amino group in the peri-position and
provide cyclic methanetriamine intermediate 21. Subsequent
acid-mediated elimination of phosphorylated hydroxylamine is
expected to provide 6-amino-1H-perimidine 13 (Scheme 3),
which should react further according to the mechanism, depic-
ted in Scheme 2, ultimately yielding the target 6H-pyrrolo-
[2,3,4-gh]perimidines 18. Gratifyingly, this multistep cascade
transformation proceeded as planned. Reactions of 19 with
excess (3.1 equiv.) nitromethane (6a) or nitroethane (6b)
afforded products 18aa and 18bb, respectively, in good yields
(Scheme 3).
We also envisioned an alternative method for the in situ
generation of key intermediate 13 employing a PPA-assisted
Schmidt reaction of perimidines 25 in the presence of sodium
azide. It is believed, that hydrazoic acid generated under
these reaction conditions, reacts with PPA to form phosphar-
azidic acid 22, which after protonation provides phosphono-
triazynium ion 24, that exists in equilibrium with tautomer 23
(Scheme 4). Species 24 can be viewed as the stabilized form
of N-amino-diazonium, and it’s reactivity reminds that of
diazonium salts.9 In particular, it can participate in efficient
SEAr-reaction with electron-rich aromatic compounds, such as
perimidines 25 to afford the corresponding (aryltriaz-1-en-1-
yl)phosphonic acids 26 (existing in equilibrium with tautomeric
18gb: R1 = 4-C6H4OMe, R2 = Me (52%);
18hc: R1 = 4-C6H4Cl, R2 = Ph (64%);
Scheme 2
condensation processes. Adjusting the content of P2O5 in PPA
affects both effective acidity and anhydridic activity of this
medium, allowing for fine-tuning of the reaction conditions
and intelligent design of multi-step processes. Furthermore,
an in situ phosphorylation of various functional groups can be
used as a temporary protection or to modify reactivity, for
example, to equip good leaving group or totally alter the
function’s normal reactivity pattern. Thus, we previously
demonstrated7,8 that normally nucleophilic nitroalkanes 6 can
be stabilized by phosphorylation as highly electrophilic aci-
forms 12 (Scheme 2). We reasoned, that generation of this
species in the presence of 6-amino-1H-perimidines 13 would
trigger an electrophilic attack at C-7 to afford (azanediyl)bis-
(phosphoric acid) 14, which after elimination of H3PO4 at low
pH would provide the protonated form of phosphorylated
oxime 15 (Scheme 2). Intramolecular 5-exo-trig nucleophilic
attack of the aniline function and subsequent elimination of
phosphorylated hydroxylamine would provide species 17,
which after deprotonation and rearomatization would yield
the desired 6H-pyrrolo[2,3,4-gh]perimidine 18 (Scheme 3). To
test this idea we subjected 6-amino-1H-perimidine (13a) to the
reaction with an excess of nitromethane (6a). First, the
o
mixture was stirred in 86% PPA at 80-90 C, then the reaction
was forced to completion at 130-140 C. The expected 6H-
pyrrolo[2,3,4-gh]perimidine (18aa) was formed as the sole
product in good preparative yield (Scheme 3). Similarly,
nitroethane (6b), α-nitrotoluenes (6c,f-h), 2-phenylnitroethane
o
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O
DOI: 10.1039/C6RA17269E
O
O
N3
H
O
PO(OH)2
NaN3 + PPA
N
N
N
P
O
P
O
Me
NaN3
PPA
Me
OH
OH
22
N
N
O
O
O
O
R2
28a: R2 = H; 28b: R2 = Me;
N
H
N
R2
N
H
HN
N
N
P
O
P
O
N
N
P
O
P
O
H
29
OH
OH
OH
OH
24
23
28c: R2 = Ph; 28d: R2 = 4-C6H4Cl;
Schmidt
rearrangement
OPO(OH)2
N
NHAc
R1
R1
N
NHAc
25a: R2 = H;
25b: R2 = Me;
25c: R2 = Ph
SEAr
OPO(OH)2
PPA
R2
N
H
N
OPO(OH)2
N
N
OPO(OH)2
R2
N
H
R2
N
H
30
31
O
O
H
N
N
N
P
O
P
O
- H3PO4
Ac
N
OH
OH
R1
N
N
Ac
R2
N
H
NH
26
OPO(OH)2
R1
N
H2
N
R2
N
H
N
OPO(OH)2
H
R2
N
H
33
OP(O)(OH)2
O
P
O
P
32
H3O
-N2
H
N
N
N
O
O
- NH2OPO(OH)2
- H3PO4
N
OH
OH
-H3PO4
R2
N
H
Ac
N
27
NH
R1
R1
R1
H3O
N
N
R2
N
34
NH2
NH
18
R2
N
N
R1
NO2
N
18aa: R1 = R2 = H (61%);
18da: R1 = CH2Ph, R2 = H (61%);
18db: R1 = CH2Ph, R2 = Me (68%);
18dc: R1 = CH2Ph, R2 = Ph (69%);
18ea: R1 = n-C5H11, R2 = H (63%);
R2
N
R2
N
18ab: R1 = H, R2 = Me (63%);
18ac: R1 = H, R2 = Ph (67%);
18ba: R1 = Me, R2 = H (68%);
18bb: R1 = R2 = Me (69%);
18bc: R1 = Me, R2 = Ph (73%);
18bd: R1 = Me, R2 = 4-C6H4Cl (63%);
18ca: R1 = Ph, R2 = H (55%);
PPA
18
H
13a: R2 = H;
13b: R2 = Me;
13c: R2 = Ph
18ac: R1 = H, R2 = Ph (62%);
18ba: R1 = Me, R2 = H (64%);
18bb: R1 = R2 = Me (63%);
18bc: R1 = Me, R2 = Ph (67%);
18ca: R1 = Ph, R2 = H (48%);
18db: R1 = CH2Ph, R2 = Me (63%);
18bc: R1 = CH2Ph, R2 = Ph (62%);
18ed: R1
=
n-C5H11, R2 = 4-C6H4Cl (58%);
18fb: R1 = 3-C6H4Cl, R2 = Me (57%);
18fc: R1 = 3-C6H4Cl, R2 = Ph (71%);
18gb: R1 = 4-C6H4OMe, R2 = Me (59%);
18hc: R1 = 4-C6H4Cl, R2 = Ph (56%);
Scheme 5
Scheme 4
nucleophilic 5-exo-trig cyclization affording tetracyclic
intermediate 33, which after elimination of O-phosphoryl
hydroxylamine would yield N-acetylpyrroloperimidine 34.
Aqueous work up accompanied with hydrolytic cleavage of N-
acetyl moiety would finally afford the target material 18. This
process design worked smoothly, as shown by a series of one-
pot reactions involving 6-acylperimidines 28a-d and nitro-
alkanes 6a-h, which led to formation of the corresponding
pyrroloperimidines in good yields (Scheme 5).
Finally, we investigated the possibility to develop a multi-
step cascade transformation involving an even more afford-
able starting material, 1,8-naphthalenediamine (28). It was
anticipated that in the presence of aci-form, generated upon
phosphorylation of nitroethane (6b), two amino groups would
be used to assemble a heterocyclic ring of perimidine 25b
(Scheme 6). This process would involve a two-fold nucleophilic
attack by nitrogen atoms and it’s mechanism would be
identical to the one previously described in Scheme 3. We
also expected that the excess of aci-form would serve as an
electrophile in the subsequent acetamidation reaction, that
form 27). Acid-mediated decomposition of these species,
accompanied with a evolution of nitrogen gas would afford
intermediate 6-aminopiperidine 13, that can be consumed in
a subsequent one-pot reaction with an appropriate nitro-
alkane. We were pleased to discover, that this process design
was viable, and the corresponding 6H-pyrrolo[2,3,4-gh]perim-
idines 18 were produced in very good yield (Scheme 4).
Next, we decided to elaborate on the one-pot preparation
of target heteroaromatic tetracycles starting from readily
available 6-acylperimidines.
nucleophilic addition of the azide across C=O bond would
provide O-phosphorylated 1-azidoalcohol 29, which should
undergo facile Schmidt rearrangement to provide acetamide
30. The subsequent addition of nitroethane 6 and in situ
generation of electrophilic aci form 12 would invoke alkylation
of 30 at C-7 to yield intermediate 31, which, after elimination
of H3PO4 would provide phosphorylated oxime 32 (shown in
Scheme 5 in protonated form). We reasoned, that the
acetamide group in 32 could be further involved in
It was expected, that initial
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c,12 were prepared according to the literature procedures. All
other reagents and solvents were purchased from commercial
Me
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DOI: 10.1039/C6RA17269E
NH2 NH2
OPO(OH)2
Me
N
HN
N
vendors and used as received.
OPO(OH)2
PPA
-H3PO4
25b
Preparation of 2-(4-chlorophenyl)-6(7)-acetylperimedine
(28d): Anhydrous aluminum chloride (1.33 g, 10.0 mmol) and
acetyl chloride (85 μL, 94 mg, 1.2 mmol) were vigorously
stirred in dry dichloromethane (20 mL) for 30 min at room
temperature. 2-(4-Chloro)phenylperimidine (279 mg, 1.0
mmol) was added by portions over 15 min, and the stirring was
continued for 30 min. The formed solution was poured into
cold water (20 mL) and dichloromethane was removed in
vacuum. Solid precipitate was filtered off and re-crystallized
from ethanol to afford the titled compound as carrot-orange
crystals. Yield 295 mg (0.92 mmol, 92%), mp 236-238 °C
(EtOH); 1H NMR (400 MHz, DMSO-d6): δ 2.57 (3H, s, CH3), 6.75
(1H, d, J = 8.1 Hz, H-4(9)), 6.97 (1H, d, J = 7.2 Hz, H-9(4)), 7.47
(1H, dd, J = 8.7, 7.2 Hz, H-8(5)), 7.67 (2H, d, J = 8.6 Hz, Ar (H-
3,5)), 8.09 (3H, m, H-5(8), Ar (H-2,6)), 8.56 (1H, d, J = 8.7 Hz, H-
7(6)), 11.39 (1H, br. s, NH); 13C NMR (100 MHz, DMSO-d6): δ
35
OPO(OH)2
PPA
-H3PO4
Me
N
OPO(OH)2
Me
H
OPO(OH)2
N
Me
N
Beckmann
rearrangement
O
N
N
Me
N
H
N
H
Me
36
30b
NH
Me
as in Scheme 5
PPA
N
Me
N
18bb (34%)
Scheme 6
should be directed to C-6 of perimidine.7 This reaction 28.6, 106.2, 111.4, 118.8, 121.2, 123.6, 127.7, 128.6(2C), 129.1
involves an initial alkylation of the activated heteroaromatic (2C), 130.9, 132.6, 136.0, 136.5, 140.6, 145.4, 151.8, 197.5; FT-
compound to form phosphorylated ketoxim 29, which upon IR (NaCl, cm-1): 3320 (NH), 2390, 1650 (CO), 1551, 1455, 1250,
heating in PPA should undergo Beckmann rearrangement to 820; HRMS (TOF-ES): Calcd. for C19H14ClN2O (M+H), 321.0789,
afford acetanilide 30b (Scheme 6). The following transform- Found 321.0784 (1.6 ppm).
ation would proceed according to the mechanism outlined in
General procedure for preparation of pyrrolo[2,3,4-
gh]perimidines from 6-aminoperimidines (Method A): A
mixture of 6-aminoperimidine 13 (1.00 mmol), nitroalkane 6
(2.10 mmol), and 86% PPA (3-4 g) was vigorously stirred for 1 h
at 80-90 oС, then heated to 130-140oС, and stirred for
additional 3 h. The reaction mixture was poured out into
stirred cold water (30 mL), and the mixture was basified with
aqueous ammonia to pH 8. Formed precipitate was filtered
Scheme 5 to afford the pyrroloperimidine core. We tested this
transformation on a single example, and were thrilled to find
that compound 18bb was formed as sole isolable product,
albeit in somewhat marginal yield (Scheme 5).
Conclusions
We have designed a series one-pot and cascade transform- off, the supernatant solution was extracted with toluene (3 x
50 mL). The precipitate was also extracted for 5 h with
toluene (100 mL) in Soxhlet apparatus. Combined organic
extracts were evaporated and the residual solid was re-
crystallized.
ations involving an unusual electrophilic behavior of poly-
phosphoric acid-activated nitroalkanes. These processes
involved PPA-mediated Schmidt and Beckmann rearrange-
ments, reactions of direct electrophilic amination with azides
and acetamidation with nitroalkanes, and N-Nef reaction. For
the first time these steps are arranged in multi-step one-pot
processes of increased complexity. The versatility of PPA as an
“intelligent” reaction media was showcased.
General procedure for preparation of pyrrolo[2,3,4-gh]perim-
idines from 1,4,8-naphthalenetriamine (Method B): A mixture
of 1,4,8-triaminonaphthalene 19 (0.173 г, 1.00 ммоль), nitro-
alkane 6 (3.10 mmol), and 86% PPA (3-4 g) was vigorously
stirred for 3 h at 80-90 °С, then heated to 130-140oС, and
stirred for additional 3 h. Aqueous work up, isolation and
purification of products is carried out in the manner described
for the Method A.
Experimental Part
1H and 13C NMR spectra were recorded on a Bruker Avance-III
spectrometer (400 or 100 MHz, respectively) equipped with
BBO probe in DMSO-d6, using TMS as internal standard. High-
resolution mass spectra were registered with a Bruker Maxis
spectrometer (electrospray ionization, in MeCN solution, using
HCO2Na–HCO2H for calibration). Melting points were
measured with a Stuart smp30 apparatus. All reactions were
performed in oven-dried 5 mL Erlenmeyer flasks open to the
atmosphere, employing overhead stirring. Reaction progress
and purity of isolated compounds were controlled by TLC on
Silufol UV-254 plates. Compounds 6f-h,10 13a-c,7c,11 and 28a-
General procedure for preparation of pyrrolo[2,3,4-gh]perim-
idines from perimidines (Method C): A mixture of perimidine
25 (1.00 ммоль), sodium azide (0.195 g, 3.00 ммоль), 86%
PPA (3-4 g) was vigorously stirred for 4 h; the reaction progress
was monitored by TLC. Then nitroalkane 6 (4.00 mmol) was
added, the temperature was raised to 110-120 oС and the
sirring was continued for additional 5 h. Aqueous work up,
isolation and purification of products is carried out in the
manner described for the Method A.
General procedure for preparation of pyrrolo[2,3,4-gh]perim-
idines from 6-acetylperimidines (Method D): A mixture of 6-
acetylperimidine 28 (1.00 ммоль), sodium azide (0.070 g, 1.07
4 | J. Name., 2012, 00, 1-3
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mmol) in 86% PPA (2-3 g) was vigorously stirred for 1 h at 55- 9.0 Hz, H-4), 8.71 (2H, d, J = 8.4 Hz, Ph(H-2,6)), 13.1 (1H, br. s,
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13
DOI: 10.1039/C6RA17269E
60 С. Then notroalkane 6 was added (2.00 mmol), and the NH); C NMR (100 MHz, DMSO-d6): δ 12.4, 112.7, 112.9,
temperature was increased to 110-120 oС (90-100 oС for 117.1, 120.5, 120.6, 120.7, 124.9, 128.1 (2C), 128.2 (2C), 129.4,
reactions with nitromethane) and the stirring was continued 130.9, 136.2, 140.1, 147.9, 155.1, 159.6.
for additional 3 h. Aqueous work up, isolation and purification
of products is carried out in the manner described for the
Method A.
2-(4-Chlorophenyl)-7-methyl-6H-pyrrolo[2,3,4-gh]perimidine
(18bd): yellowish orange crystals, mp 243-245 °C (toluene); Rf
1
0.73 (EtOAc); H NMR (400 MHz, CDCl3): δ 2.97 (3H, s, Me),
Preparation of 2,7-dimethylpyrrolo[2,3,4-gh]perimidine from 7.51 (1H, d, J = 8.6 Hz, Ar (H-3,5)), 7.76 (1H, d, J = 9.2 Hz, H-3),
1,8-diaminonaphthalene (Method E): A mixture of 1,8-di- 7.95 (1H, d, J = 8.8 Hz, H-9), 8.14 (1H, d, J = 8.8 Hz, H-4), 8.27
aminonaphthalene (35) (0.158 g, 1.00 mmol), nitroalkene 6 (1H, d, J = 9.2 Hz, H-8), ), 8.68 (2H, d, J = 8.6 Hz, Ar (H-2,6)),
(2.10 mmol), and 86% PPA (2-3 g) was vigorously stirred for 3 h 9.59 (1H, br. s, NH); 13C NMR (100 MHz, CDCl3): δ 29.8, 113.5,
at 90-100 ; the reaction progress was monitored by TLC, 113.8, 119.2, 119.8, 121.5, 123.1, 125.2, 128.8 (2C), 130.7,
eluting with EtOAc/EtOH mixture, 1:1). Then, the temperature 130.2 (2C), 133.9, 135.8, 139.2, 148.9, 156.4, 160.8; FT-IR
was increased to 140-150 oС and the stirring was continued for (NaCl, cm-1): 33907 (NH), 2991, 1621, 1552, 1491, 1360, 1275,
additional 3 h. Aqueous work up, isolation and purification of 1181, 1080, 840, 800; HRMS (TOF-ES): Calcd. for C19H13ClN3
products is carried out in the manner described for the (M+H) 318.0793, Found 318.0788 (1.6 ppm).
7-Phenyl-6H-pyrrolo[2,3,4-gh]perimidine (18ca):6b yellowish
Method A.
1
6H-Pyrrolo[2,3,4-gh]perimidine (18aa):6b yellowish orange orange crystals, mp 263-265 °C (toluene); H NMR (400 MHz,
1
crystals, mp 207-209 °C (toluene); H NMR (400 MHz, DMSO- DMSO-d6): δ 7.54 (3H, m, Ph(H-3,4,5)), 7.66 (1H, d, J = 9.0 Hz,
d6): δ 7.70 (1H, d, J = 9.0 Hz, H-3), 7.91 (1H, d, J = 8.7 Hz, H-9), H-3), 7.79 (1H, d, J = 8.7 Hz, H-9), 8.18 (2H, d, J = 7.7 Hz, Ph (H-
8.45 (1H, d, J = 8.7 Hz, H-8), 8.46 (1H, s, H-2), 8.51 (1H, d, J = 2,6)), 8.33 (1H, d, J = 8.7 Hz, H-8), 8.69 (1H, d, J = 9.0 Hz, H-4),
9.0 Hz, H-4), 9.48 (1H, s, H-6), 13.2 (1H, br. s, NH); 13C NMR 9.33 (1H, s, H-6), 13.3 (1H, br. s, NH); 13C NMR (100 MHz,
(100 MHz, DMSO-d6): δ 111.9, 112.9, 116.3, 120.1, 120.4, DMSO-d6): δ 112.0, 112.2, 117.9, 120.9, 121.2, 122.3, 126.2,
120.6, 124.9, 131.1, 136.4, 147.8, 154.9, 163.0.
127.2 (2C), 128.5, 129.3 (2C), 129.4, 131.0, 132.2, 148.4, 154.6,
2-Methyl-6H-pyrrolo[2,3,4-gh]perimidine (18ab):6b yellowish
163.5.
1
orange crystals, mp 237-238 °C (toluene); H NMR (400 MHz, 7-Benzyl-6H-pyrrolo[2,3,4-gh]perimidine (18da): yellowish
DMSO-d6): δ 2.93 (3H, s, Me), 7.65 (1H, d, J = 9.0 Hz, H-3), 7.82 orange crystals, mp 251-252 °C (toluene); H NMR (400 MHz,
1
(1H, d, J = 8.7 Hz, H-9), 8.42 (1H, d, J = 8.7 Hz, H-8), 8.46 (1H, s, DMSO-d6): δ 4.72 (2H, s, CH2), 7.24 (1H, t, J = 7.4 Hz, Ph (H-4)),
H-2), 8.50 (1H, d, J = 9.0 Hz, H-4), 13.1 (1H, br. s, NH); 13C NMR 7.34 (2H, dd, J = 7.8, 7.4 Hz, Ph (H-3,5)), 7.42 (2H, d, J = 7.8 Hz,
(100 MHz, DMSO-d6): δ 26.9, 111.9, 112.9, 116.3, 119.9, 120.5, Ph (H-2,6)), 7.58 (1H, d, J = 9.1 Hz, H-3), 7.81 (1H, d , J = 8.8 Hz,
120.6, 124.7, 130.8, 136.3, 147.8, 154.9, 163.0.
H-9), 8.32 (1H, d, J = 9.1 Hz, H-8), 8.35 (1H, d, J = 8.8 Hz, H-4),
9.39 (1H, s, H-6), 13.35 (1H, br. s, NH); 13C NMR (100 MHz,
DMSO-d6): δ 33.4, 113.0, 114.2, 117.7, 120.4, 121.2, 125.2,
126.6, 126.8 (2C), 128.5, 129.7, 129.8, 131.2 (2C), 130.9, 139.0,
147.7, 155.0; FT-IR (NaCl, cm-1): 3407 (NH), 3214, 3028, 2814,
1618, 1494, 1373; HRMS (TOF-ES): Calcd. for C19H14N3 (M+H),
284.1182, Found 284.1180 (0.9 ppm).
2-Phenyl-6H-pyrrolo[2,3,4-gh]perimidine (18ac):6b yellowish
orange crystals, mp 201– 203 °C (toluene); 1H NMR (400 MHz,
DMSO-d6): δ 7.57–7.63 (m, 3H, Ph(H- 3,4,5)), 7.78 (d, J = 8.4
Hz, 1H, H-3), 7.96 (d, J = 8.5 Hz, 1H, H-9), 8.39 (s, 1H, H- 2),
8.43 (d, J=8.5Hz, 1H, H-8), 8.51 (d, J=8.4Hz, 1H, H-4), 8.73 (d,
J=7.3Hz, 2H, Ph(H-2,6)), 13.1 (br s, 1H, NH). 13C NMR (100
MHz, DMSO-d6): δ 112.51, 112.88, 117.14, 120.51, 120.55, 7-Benzyl-2-methyl-6H-pyrrolo[2,3,4-gh]perimidine
120.72, 124.83, 128.08 (2C), 128.20 (2C), 129.32, 130.86, yellowish orange crystals, mp 223-225 °C (toluene); H NMR
(18db):
1
136.28, 140.12, 147.93, 155.14, 160.14.
7-Methyl-6H-pyrrolo[2,3,4-gh]perimidine (18ba):6b yellowish
orange crystals, mp 259-260 °C (toluene); H NMR (400 MHz,
DMSO-d6): δ 2.98 (3H, s, Me), 7.58 (1H, d, J = 9.0 Hz, H-3), 7.78
(1H, d, J = 8.7 Hz, H-9), 8.31 (1H, d, J = 8.7 Hz, H-8), 8.47 (1H, d,
J = 9.0 Hz, H-4), 9.36 (1H, s, H-6), 13.1 (1H, br. s, NH); 13C NMR
(100 MHz, DMSO-d6): δ 12.5, 112.0, 112.9, 116.3, 120.1, 120.5,
120.5, 124.7, 130.8, 136.2, 147.8, 155.0, 163.0.
2,7-Dimethyl-6H-pyrrolo[2,3,4-gh]perimidine (18bb):6b yell-
owish orange crystals, mp 271-272 °C (toluene); H NMR (400
MHz, DMSO-d6): δ 2.86 (3H, s, 7-Me), 2.92 (3H, s, 2-Me), 7.46
(1H, d, J = 9.0 Hz, H-3), 7.64 (1H, d, J = 8.7 Hz, H-9), 8.22 (1H, d,
J = 8.7 Hz, H-8), 8.38 (1H, d, J = 9.0 Hz, H-4), 13.1 (1H, br. s,
NH); 13C NMR (100 MHz, DMSO-d6): δ 12.4, 27.0, 112.0, 112.8,
116.2, 120.0, 120.4, 120.5, 124.6, 130.7, 136.1, 147.7, 154.9,
162.9.
7-Methyl-2-phenyl-6H-pyrrolo[2,3,4-gh]perimidine (18bc):6b
yellowish orange crystals, mp 245-246 °C (toluene/petroleum
ether); 1H NMR (400 MHz, DMSO-d6): δ 2.93 (s, 3H, Me), 7.48–
7.58 (3H, m, Ph(H-3,4,5)), 7.62 (1H, d, J = 9.0 Hz, H-3), 7.82 (1H,
d, J = 8.7 Hz, H-9), 8.29 (1H, d, J = 8.7 Hz, H-8), 8.43 (1H, d, J =
(400 MHz, DMSO-d6): δ 2.86 (3H, s, Me), 4.68 (2H, s, CH2), 7.23
(1H, t, J = 7.3 Hz, Ph (H-4)), 7.33 (2H, dd, J = 7.7, 7.3 Hz, Ph (H-
3,5)), 7.43 (2H, d, J = 7.7 Hz, Ph (H-2,6)), 7.48 (1H, d, J = 9.1 Hz,
H-3), 7.69 (1H, d , J = 8.8 Hz, H-9), 8.24 (1H, d, J = 9.1 Hz, H-8),
8.27 (1H, d, J = 8.8 Hz, H-4), 13.12 (1H, br. s, NH); 13C NMR
(100 MHz, DMSO-d6): δ 27.1, 33.2, 112.1, 112.6, 117.0, 120.5,
120.7, 120.8, 124.9, 126.6, 127.5, 128.2, 128.7 (2C), 128.9 (2C),
130.9, 138.9, 155.0, 163.2; FT-IR (NaCl, cm-1): 3387 (NH),
3069, 2793, 2345, 1501, 1367; HRMS (TOF-ES): Calcd. for
C20H16N3 (M+H) 298.1339, Found 298.1343 (1.3 ppm).
1
1
7-Benzyl-2-phenyl-6H-pyrrolo[2,3,4-gh]perimidine
(18dc):
1
yellowish orange crystals, mp 195-197 °C (toluene); H NMR
(400 MHz, DMSO-d6): δ 4.72 (2H, s, CH2), 7.25 (1H, t, J = 7.4 Hz,
Ph (H-4)), 7.34 (2H, dd, J = 7.7, 7.4 Hz, Ph (H-3,5)), 7.45 (2H, d, J
= 7.7 Hz, Ph (H-2,6)), 7.49–7.57 (m, 3H, Ph(H- 3,4,5)), 7.65 (1H,
d, J = 9.1 Hz, H-3), 7.87 (1H, d, J = 8.8 Hz, H-9), 8.33 (1H, d, J =
9.1 Hz, H-8), 8.35 (1H, d, J = 8.8 Hz, H-4), 8.69 (2H, dd, J = 8.5,
1.6 Hz, Ph(H-2,6)), 13.31 (1H, br. s, NH); 13C NMR (100 MHz,
DMSO-d6): δ 33.4, 113.0, 118.1, 120.8, 121.4, 121.6, 125.4,
126.9, 128.3 (2C), 128.6 (2C), 128.9 (2C), 129.1 (2C), 129.8,
130.9, 131.4, 138.9, 139.0, 140.2, 148.3, 155.3, 160.0; FT-IR
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
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PleaseRdSoCnoAtdavdajnusctems argins
Page 6 of 8
ARTICLE
Journal Name
(NaCl, cm-1): 3373 (NH), 2924, 2842, 2366, 1745, 1625, 1535, 8.70 (1H, d, J = 9.2 Hz, H-8), 13.43 (1H, br. s, NH); 13C NMR
View Article Online
DOI: 10.1039/C6RA17269E
1497, 1367, 1342, 1274; HRMS (TOF-ES): Calcd. for C25H18N3 (100 MHz, DMSO-d6): δ 27.6, 55.9, 111.8, 112.8, 115.6 (2C),
(M+H) 360.1495, Found 360.1501 (1.6 ppm).
118.4, 121.1, 121.7, 122.5, 124.7, 126.1, 129.2 (2C), 132.0,
136.3, 148.8, 155.2, 160.3, 164.0; FT-IR (NaCl, cm-1): 3097
(NH), 2938, 1611, 1556, 1490, 1373, 1253, 1181, 1022; HRMS
(TOF-ES): Calcd. for C20H16N3O (M+H) 314.1288, Found
314.1285 (1.0 ppm).
7-Pentyl-6H-pyrrolo[2,3,4-gh]perimidine (18ea): yellowish
orange crystals, mp 156-158 °C (toluene-petroleum ether); Rf
1
0.62 (EtOAc/EtOH 3:1); H NMR (400 MHz, DMSO-d6): δ 0.87
(3H, t, J = 7.0 Hz, Me), 1.36 (4H, m, CH2CH2), 1.93 (2H, m, CH2),
3.36 (2H+H2O, m, CH2+H2O), 7.60 (1H, d, J = 9.1 Hz, H-3), 7.80 7-(4-Chlorophenyl)-2-phenyl-6H-pyrrolo[2,3,4-gh]perimidine
(1H, d, J = 8.7 Hz, H-9), 8.35 (1H, d, J = 8.7 Hz, H-4), 8.52 (1H, d, (18hc): yellowish orange crystals, mp 172-174 °C (toluene/
J = 9.1 Hz, H-8), 9.38 (1H, s, H-6), 13.24 (1H, br. s, NH); 13C petroleum ethar); Rf 0.80 (EtOAc); 1H NMR (400 MHz, DMSO-
NMR (100 MHz, DMSO-d6): δ 13.8, 20.7, 21.8, 29.4, 31.0, d6): δ 7.50-7.60 (3H, m, Ph (H-3,4,5)), 7.72 (2H, d, J = 8.6 Hz, Ar
111.7, 114.1, 117.0, 120.2, 120.5, 120.7, 124.8, 131.1, 140.7, (H-3,5)), 7.87 (1H, d, J = 9.2 Hz, H-3), 8.00 (1H, d, J = 8.8 Hz, H-
147.4, 154.6, 154.8; FT-IR (NaCl, cm-1): 3507 (NH), 2958, 2438, 9), 8.24 (2H, d, J = 8.6 Hz, Ar (H-2,6)), 8.33 (1H, dd, J = 8.8, J =
1631, 1572, 1490, 1255, 1190, 1082; HRMS (TOF-ES): Calcd. for 6.8, Hz, ArH), 8.43 (1H, d, J = 8.8 Hz, H-8), 7.82 (1H, d, J = 9.2
C17H18N3 (M+H) 264.1495, Found 264.1493 (0.8 ppm).
Hz, H-4), 13.71 (1H, br. s, NH); 13C NMR (100 MHz, DMSO-d6):
δ 112.4, 112.9, 119.9, 121.1, 121.6, 123.4, 126.5, 126.9, 128.2
(2C), 128.5 (2C), 128.9 (2C), 129.6 (2C), 129.8, 130.5, 131.6,
133.4, 139.8, 148.7, 154.6, 160.2; FT-IR (NaCl, cm-1): 3350
(NH), 2995, 2850, 2380, 1570, 1361, 1240, 1150, 800, 700;
HRMS (TOF-ES): Calcd. for C24H15ClN3 (M+H) 380.0949, Found
380.0944 (1.3 ppm).
2-(4-Chlorophenyl)-7-pentyl-6H-pyrrolo[2,3,4-gh]perimidine
(18ed): yellowish orange crystals, mp 211-213 °C (toluene/
petroleum ether); Rf 0.74 (EtOAc); 1H NMR (400 MHz, CDCl3): δ
0.92 (3H, t, J = 7.1 Hz, Me), 1.35-1.47 (4H, m, CH2CH2), 1.93-
2.00 (2H, m, CH2), 3.30 (2H, J = 7.7 Hz, CH2), 7.51 (1H, d, J = 8.6
Hz, Ar (H-3,5)), 7.78 (1H, d, J = 9.2 Hz, H-3), 7.97 (1H, d, J = 8.8
Hz, H-9), 8.16 (1H, d, J = 8.8 Hz, H-4), 8.30 (1H, d, J = 9.2 Hz, H-
8), ), 8.69 (2H, d, J = 8.6 Hz, Ar (H-2,6)), 9.71 (1H, br. s, NH); 13C
NMR (100 MHz, CDCl3): δ 13.9, 22.4, 28.0, 29.8, 31.6, 113.3,
113.5, 119.0, 119.7, 121.4, 122.8, 124.9, 128.6 (2C), 130.1 (2C),
130.3, 135.7, 139.0, 139.1, 148.6, 156.1, 160.6; FT-IR (NaCl,
cm-1): 33907 (NH), 2991, 1621, 1552, 1491, 1360, 1275, 1181,
1080, 840, 800; HRMS (TOF-ES): Calcd. for C23H21ClN3 (M+H)
374.1419, Found 374.1423 (1.1 ppm).
Acknowledgements
Financial support for this work was provided by Russian
Foundation for Basic Research (grants #16-03-00177a and 16-
3300483 mol_a).
7-(3-Chlorophenyl)-2-methyl-6H-pyrrolo[2,3,4-gh]perimidine
(18fb): yellowish orange crystals, mp 283-284 °C (toluene); Rf
0.44 (EtOAc/EtOH 3:1); 1H NMR (400 MHz, CDCl3): δ 3.00 (3H,
s, Me), 7.37 (1H, d, J = 7.9 Hz, Ar (H-4)), 7.45 (1H, dd, J = 7.9, J
= 7.7 Hz, Ar (H-5)), 7.68 (1H, d, J = 9.2 Hz, H-3), 7.75 (1H, d, J =
8.8 Hz, H-9), 7.82 (1H, d, J = 7.7 Hz, Ar (H-6)), 7.92 (1H, s, Ar (H-
2)), 8.00 (1H, d, J = 8.8 Hz, H-4), 8.40 (1H, d, J = 9.2 Hz, H-8),
9.51 (1H, br. s, NH); 13C NMR (100 MHz, CDCl3): δ 25.8, 111.4,
112.1, 117.9, 119.8, 122.0, 124.3, 125.3, 126.1, 127.7, 129.8,
130.0, 132.4, 133.6, 134.5, 134.8, 147.0, 153.6, 162.6; FT-IR
(NaCl, cm-1): 3317 (NH), 2985, 2825,2240, 1641, 1554, 1490,
1383, 1273, 1181, 840, 800; HRMS (TOF-ES): Calcd. for
C19H13ClN3 (M+H) 318.0793, Found 318.0787 (1.9 ppm).
Notes and references
7-(3-Chlorophenyl)-2-phenyl-6H-pyrrolo[2,3,4-gh]perimidine
(18fc): yellowish orange crystals, mp 150-152 °C (toluene/
petroleum ether); Rf 0.75 (EtOAc); H NMR (400 MHz, DMSO-
1
1
2
See, for example: (a) I. Gutman, M. Milun, N. Trinajstic,
J. Am. Chem. Soc. 1977, 99, 1692; (b) P. Weilmunster,
A. Keller, K.-H. Homann, Combust. Flame 1998, 116, 62;
(c) R. Vianello, Z. B. Maksic, Eur. J. Org. Chem. 2005,
3571; (d) Y.-C. Chang, I. Chao, J. Phys. Chem. Lett.
2010, 1, 116.
d6): δ 7.51-7.66 (5H, m, ArH), 7.67 (1H, d, J = 9.2 Hz, H-3), 7.79
(1H, d, J = 8.8 Hz, H-9), 7.92-7.95 (2H, m, ArH), 8.33 (1H, dd, J =
8.8, J = 6.8, Hz, ArH), 8.69-8.73 (3H, m, ArH), 13.62 (1H, br. s,
NH); 13C NMR (100 MHz, DMSO-d6): δ 112.8, 113.0, 120.33,
121.1, 121.6, 122.9, 123.7, 126.1, 126.5, 126.7, 128.4 (2C),
128.6 (2C), 129.9, 130.5, 131.5, 133.5, 133.8, 134.4, 140.8,
148.9, 154.6, 160.3; FT-IR (NaCl, cm-1): 3518 (NH), 2380, 1690,
1621, 1554, 1551, 1363, 1270, 800, 700; HRMS (TOF-ES): Calcd.
for C24H15ClN3 (M+H) 380.0949, Found 380.0942 (1.8 ppm).
See, for example: (a) S. K. Kim, J. H. Bok, R. A. Bartsch,
J. Y. Lee, J. S. Kim, Org. Lett. 2005, 7, 4839; (b) T. J.
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Chem. 2009, 74, 4855; (d) H. Maeda, T. Maeda, K.
Mizuno, K. Fujimoto, H. Shimizu, M. Inouye, Chem. Eur.
7-(4-Methoxyphenyl)-2-methyl-6H-pyrrolo[2,3,4-gh]perimid-
ine (18gb): yellowish orange crystals, mp 277-279 °C (toluene);
Rf 0.32 (EtOAc:EtOH 3:1); 1H NMR (400 MHz, DMSO-d6): δ 2.89
(3H, s, Me), 3.88 (3H, s, OMe), 7.21 (2H, d, J = 8.6 Hz, Ar (H-
3,5)), 7.63 (1H, d, J = 9.2 Hz, H-3), 7.75 (1H, d, J = 8.7 Hz, H-9),
8.14 (2H, d, J = 8.6 Hz, Ar (H-2,6)), 8.30 (1H, d, J = 8.7 Hz, H-4),
J. 2006, 12, 824;
(e) J. Xie, M. Menand, S.
Maisonneuve, R. Metivier, J. Org. Chem. 2007, 72,
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3
See, for reviews: (a) I. V. Borovlev, O. P. Demidov,
Chem. Heterocycl. Comp. 2003, 39, 1417; (b) I. V.
6 | J. Name., 2012, 00, 1-3
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RSC Advances
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Journal Name
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DOI: 10.1039/C6RA17269E
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(a) N. A. Aksenov, A. V. Aksenov, O. N. Nadein, D. A.
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DOI: 10.1039/C6RA17269E
Rational Design of an Efficient One-Pot Synthesis of 6H-
pyrrolo[2,3,4-gh]perimidines in Polyphosphoric Acid†
Alexander V. Aksenov,*a Nicolai A. Aksenov,a,b Dmitrii S. Ovcharov,a Dmitrii A. Aksenov,a
Georgii Griaznov,a Leonid G. Voskressensky,b and Michael Rubin*a,c
TOC entry
Several highly efficient one-pot synthetic protocols were developed, enabling
polyphosphoric acid-activated nitroalkanes to act as electrophiles in reactions with
aminonapthalenes.