Received: 4 December 2021 Revised: 26 January 2022 Accepted: 1 February 2022

DOI: 10.1002/jhet.4459

ARTICLE

Efficient synthesis of benzo[h]carbazol[3,2-b][1,6]

naphthyridines

Yamuna Ezhumalai1 | Prabakaran Kumaresan2 | Zeller Matthias3 |

Rajendra Prasad Karnam Jayarampillai4

1
Department of Chemistry, Karpagam
Academy of Higher Education, Abstract
Coimbatore, India The use of CuI as a promoter to examine amination in the reaction of
2
Department of Chemistry, PSG College of aminocarbazole (1) and 2-methyl-4-chloroquinoline (2) resulted in a
Arts and Science, Coimbatore, India
functionalized series of substituted naphthylamino carbazole. After cyclization
3
Department of Chemistry, Purdue
University, West Lafayette, Indiana, USA
with polyphosphoric acid and benzoic acid/p-toluic acid, new isomeric
4
Department of Chemistry, Bharathiar ellipticine derivatives of linear benzo[h]carbazol[3,2-b][1,6]naphthyridines
University, Coimbatore, India were obtained in high yield. The current method has the advantages of a
straightforward methodology, a clean and mild reaction, a broad substrate
Correspondence
Rajendra Prasad Karnam Jayarampillai, range, and a high yield.
Department of Chemistry, Bharathiar
University, Coimbatore-641046, India.
Email: [email protected]

Funding information
Indian Institute of Science; the Indian
Institute of Technology Madras

1 | INTRODUCTION widespread interest in ellipticine analogs, little research

has been done on the production and fusion of ellipticine
A wide variety of nitrogen-containing natural products with other therapeutically useful compounds [6].
have been found all over the world and exhibited a broad The strong DNA binding affinity of 1,6-naphthyridines
range of biological properties [1]. In particular, ellipticine is considered to be at least partially important for their
has been demonstrated to be effective in treating various therapeutic benefits [7]. The 1,6-naphthyridine moiety is a
diseases, especially osteolytic breast cancer metastases major pharmacophore found in a wide range of naturally
and brain tumors (Figure 1) [2]. Ellipticine and its deriva- occurring and synthetically created pharmaceutical sub-
tives, moreover, exhibited high efficiencies against various stances [8].
types of cancers, because of their limited side effects and Despite the fact that the naphthyridine moiety is
absence of hematological toxicity. The molecular mecha- uncommon in nature, it has shown to be a useful tool for
nism of ellipticine to act as an anticancer drug molecule creating structurally varied chemical catalogs of drug-like
was initially involved through DNA binding to inhibit heterocycles [9–12]. In this connection, we aim to pre-
topoisomerases-II [3]. Therefore, ellipticine has been pare an ellipticine analog from 3-amino-9-ethylcarbazole
established to be an attractive synthesis candidate, with by amination reaction followed by cyclization.
numerous methods having been discovered [4]. Not only Among the various catalyst used for amination reaction,
ellipticine, but also hetero-annulated carbazoles, which copper-based catalysis forms C–N bonds that are more
are structurally similar, have received a lot of attention in expensive, less hazardous, and more ecological than other
the laboratory, and these congeners have a superior phar- transition metal catalysis procedures [6]. As a result of this,
macological profile than the others [5]. Despite the the amination of aryl halides by CuI has received a lot of

J Heterocyclic Chem. 2022;59:1191–1197. wileyonlinelibrary.com/journal/jhet © 2022 Wiley Periodicals LLC. 1191

1192 EZHUMALAI ET AL.

H3C H3C H3CO H3C HO H3C

CH3
N N N N

H3CCOO
N N N N
H CH3 H H CH3 H CH3
CH3

Ellipticine Olivacine 9-methoxyellipticine Celliptium

FIGURE 1 Structures of ellipticine derivatives

attention. Tandem annulations, a unique combination of aim to prepare various substituted quinolinocarbazoles, the
copper(I)iodide, and dimethylformamide have piqued inter- precursor 3-amino-9-ethylcarbazole (1) was reacted with
est due to their ease of use and strong reactivity [13,14]. 2-methyl-4-chloroquinoline (2) using CuI as a promoter
In our research lab, we have developed various hetero- (Scheme 1). On the basis of its IR and NMR spectra, the
annulated carbazoles as well as naphthyridines [12,13,15]. product was identified as 3-(N-(2-methylquinolin-4-yl)
In continuation of that, herein, we report the synthesis of amino)-9-ethyl-9H-carbazole (3).
ellipticine analog, carbazolobenzonaphthyridines from After obtaining the potential precursor 3, we focused
3-amino-9-ethylcarbazole via N-(quinolin-4-yl)-3-amino- our attention on reacting it with benzoic acid and p-toluic
9-ethylcarbazoles using Bernthsen reaction conditions. It acid thereby anticipating to obtain benzo[h][1,6]naph-
should be noted that the Bernthsen reaction yield surpris- thyridine derivatives. As a result, 3a was exposed to the
ingly, only linear product benzo[h]carbazol[3,2-b][1,6] Bernthsen reaction with benzoic acid in the presence of a
naphthyridine at a higher temperature. catalyst such as polyphosphoric acid (PPA). This reaction
was performed at two different temperatures, 60 and
100
C. Under both conditions, the reaction failed. Upon
2 | R ES U L T S A N D D I S C U S S I O N gradually raising the temperature the reaction proceeds
smoothly at 160
C, but even and after long hours (24 h)
Our research began with the creation of quinolinocarbazole- unreacted starting material 3a remains. Increasing the
based moieties suitable for the Bernthsen reaction. With the amount of benzoic acid from a 1 to a 1.5 molar ratio led

R2 R2
H
H3C N H3C N

Cl R1 R1
NH2
NH N
R1
CuI/DMF

N N CH3 K2CO3 N
N
R2

1 2 3

PPA, 160oC
R3COOH
8 hours

2,3,4,5 a) R1=CH3, R2=H

b) R1=H, R2=CH3
c) R1=Cl, R2=H R2
4,5 R3= -C6H5 R 1
H3C N
R3= -p-C6H4CH3
O
R3 R1
2
R3
N R
N
N
N
R3 CH3 N

4,5 6,7

SCHEME 1 Synthesis of 12-aroyl-9-ethyl-6-methyl-7-phenyl-9H-benzo[h]carbazol[3,2-b] [1,6]naphthyridines (4, 5)

EZHUMALAI ET AL. 1193

to complete consumption of the starting material within product of the predicted compound, 12-benzoyl-9-ethyl-
8 h at 160
C (Scheme 1). Despite the availability of two 2,6-dimethyl-7-phenyl-9H-benzo[h]carbazol[3,2-b][1,6]
active sites where cyclization could occur, either at the naphthyridine (4a). The identities of the additional
C2 position, yielding a linear product, or at the C4 posi- compounds 4b & 4c were determined in a similar manner,
tion, yielding an angular carbazole, the only formed with all spectroscopic data easily assignable. Finally, a
product was assigned as the linear isomer namely, single-crystal X-ray diffraction analysis confirmed the
12-benzoyl-9-ethyl-2,6-dimethyl-7-phenyl-9H-benzo[h] structure of one of the series members, 4a (Figure 2).
carbazol[3,2-b][1,6]naphthyridine (4a) on the basis of The aforesaid annulation reaction sequence was also
its lower melting point [16]. Benzoylation initially applied to substituted benzoic acid, namely p-toluic acid,
takes place in a more feasible C6-position of the carba- which yielded identical results 5a-c (Table 1). The reac-
zole moiety and then with an excess of benzoic acid, tion time should be significantly reliant on the benzoic
the reaction proceeds at the C3-position of quinoline to acid substituent. The presence of a methyl group at the
form the linear product [17]. Finally, the structure is para position of the phenyl ring aided reaction rate and
confirmed by crystallographic studies (Figure 2). increased product yield significantly.
In the IR spectra of 4a, the C=O and C=N groups, for In Scheme 2, the CuI catalyzed 2-methyl-
example, are responsible for the stretching frequencies at 4-chloroquinolines (2a–c) with aminocarbazole (1) are
1641 and 1600 cm1. The presence of 13-, 20 -, 60 -, 10-, and proposed as a mechanism. The oxidative addition of
4-position protons resulted in four doublets at 6.56 2-methyl-4-chloroquinolines (2a–c) with CuI is the first
(J = 2.0 Hz), 7.39 (J = 8.0 Hz), 7.57 (J = 8.0 Hz), and 8.98 step, which results in the intermediate A. Intermediate B
(J = 8.0 Hz) in its [1]H NMR spectrum. Three singlets is formed as a result of compound 1. Finally, compound
appeared at δ 8.14, δ 8.48, and δ 8.58 are because of the 3 is obtained by reductive elimination of intermediate B,
presence of 8-, 14-, and 1-position protons, respectively. and the catalyst is regenerated. In the same way, com-
The methylene and methyl protons of the ethyl group at pound 3 goes through a catalytic cycle [16].
N9 appear at δ 4.65 (J = 7.50 Hz) as a quartet and δ 1.62
(J = 7.50 Hz) as a triplet, respectively. At δ 2.86 and δ
2.53, two methyl protons emerged as two singlets. It has 2.1 | Single crystal X-ray analysis
a carbonyl carbon signal at 196.51 in its [13]C NMR spec-
trum. The molecular ion peak is located at m/z 555, and On a Bruker APEX II CCD diffractometer, diffraction
elemental analysis revealed the molecular formula to be data were collected at 100 K using monochromatic Mo K
C39H29N3O. The structure of the compound was con- radiation and the omega scan technique. To collect data
firmed by spectral and analytical data as the benzoylated for 4a, calculate its grid, then integrate and modify the

FIGURE 2 Crystal structure of

compound 4a
1194 EZHUMALAI ET AL.

TABLE 1 Synthesis of compounds 4–5

S. no Compounds R1 R2 R3 Yield (%)a

1 4a CH3 H C6H5 50
2 4b H CH3 C6H5 68
3 4c Cl H C6H5 65
4 5a CH3 H p-CH3-C6H4 65
5 5b H CH3 p-CH3-C6H4 69
6 5c Cl H p-CH3-C6H4 70
a
Isolated yield after purification by recrystallization.

H3C R2 S C H E M E 2 Proposed mechanism for

N
the formation of compound 3

NH R1
Cl
R1 CuI
3
N CH3
H
R2 2 I N
Cl I Cu
Cu R 1

R1
N CH3
N CH3 R2 B
R2 A

NH2 HCl
K2CO3
1

data for absorption and other systematic errors, the Finally, crystallographic data demonstrated that cycli-
Apex2 suite of algorithms was employed [18]. SHELXS zation occurs at the C2-position, resulting in the forma-
was used to solve the structure [19], then Shelxl2018 was tion of compound 4a.
used to improve it by employing complete matrix linear
regression versus F2 including all reflections [20]. H
atoms attached to carbon and nitrogen atoms were geo- 2.2 | Experimental section
metrically positioned and restricted to ride on their par-
ent atoms with C–H bond lengths of 0.95 for alkene and Melting points (M.p.) were obtained using a Mettler FP
aromatic C–H, 0.99 and 0.98 for aliphatic CH2 and CH3 51 apparatus (Mettler Instruments, Switzerland). They
moieties, respectively. Methyl H atoms were allowed to are measured in degrees Celsius (
C). Using KBr pellets,
spin but not tip in order to completely fit the observed IR spectra were acquired using a Shimadzu FTIR-
electron cloud. The value of Uiso (H) was set to be a mul- 8201PC spectrophotometer (Shimadzu, Japan). At IIT,
tiple of Ueq (C), with 1.5 and 1.2 units for CH3 and C–H Chennai, 1H NMR spectra were acquired using tetra-
and CH2 units, respectively. The Cambridge Crystallo- methylsilane as an internal reference on a Bruker AMX
graphic Data Centre has received complete crystallo- 500 (500 MHz) spectrometer. Parts per million are used
graphic data in CIF format. The supplemental to express chemical changes (ppm). At Bharathiar
crystallographic data for this article may be found in University's Department of Chemistry, microanalyses
CCDC 848035. The Cambridge Crystallographic Data were done on a Vario EL III model CHNS analyzer
Centre provides these data for free at www.ccdc.cam.ac. (Vario, Germany). Thin-layer chromatography was used
uk/data request/cif (Table 2). to determine the purity of the products, which were
EZHUMALAI ET AL. 1195

TABLE 2 Crystal details

Compound 4a
Crystal data
Chemical formula C39H29N3O
Mr 555.65
Crystal system, space group Triclinic, P1
Temperature (K) 100
a, b, c (Å) 9.673 (2), 9.750 (2), 16.277 (5)
α, β, γ (
) 81.525 (5), 72.744 (4), 80.511 (4)
3
V (Å ) 1438.1 (7)
Z 2
F(000) 584
Dx (Mg m3) 1.283
Radiation type Mo Kα
No. of reflections for cell measurement 3762


θ range ( ) for cell measurement 2.3–31.0
μ (mm1) 0.08
Crystal shape Plate
Color Orange
Crystal size (mm) 0.29  0.27  0.18
Data collection
Diffractometer Bruker AXS SMART APEX CCD diffractometer
Radiation source fine-focus sealed tube
Monochromator Graphite
Scan method ω scans
Absorption correction Multi-scan, Apex2 v2009.7–0 (Bruker, 2009)
Tmin, Tmax 0.680, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections 17,965, 7053, 5404
Rint 0.025
θ values (
) θmax = 28.3, θmin = 1.3
1
(sin θ/λ)max (Å ) 0.667
Range of h, k, l h = 12 ! 12, k = 12 ! 12, l = 21 ! 21
Refinement
Refinement on F2
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.127, 1.05
No. of reflections 7053
No. of parameters 391
No. of restraints 0
H-atom treatment H-atom parameters constrained
Weighting scheme w = 1/[σ2(Fo2) + (0.0631P)2 + 0.370P] where P = (Fo2 + 2Fc2)/3
(Δ/σ)max <0.001
3
Δρmax, Δρmin (e Å ) 0.35, 0.25

covered with silica gel-G and developed with petroleum India, provided the 3-amino-9-ethylcarbazole. The X-ray
ether, ethyl acetate, and methanol. Aldrich, Bangalore, diffractometer was funded by NSF Grant CHE 0087210,
1196 EZHUMALAI ET AL.

Ohio Board of Regents Grant CAP-491, and by Youngs- 40 -CH3), 2.25 (s, 3H, 400 -CH3), 2.50 (s, 3H, 6-CH3), 2.84 (s,
town State University. 3H, 2-CH3), 4.65 (q, J = 7.0 Hz, 2H, 9-CH2CH3), 6.51 (d,
J = 2.0 Hz, 1H, 13-H), 6.72 (d, J = 8.0 Hz, 2H, 30 & 50 - H),
7.27 (d, J = 8.0 Hz, 2H, 20 & 60 - H), 7.31 (d, J = 8.0 Hz,
2.3 | General procedure for 2H, 300 & 5”-H), 7.52 (d, J = 8.0 Hz, 1H, 11-H), 7.59 (d,
compounds 4/5 J = 8.0 Hz, 2H, 200 & 6”-H), 7.66 (d, J = 8.0 Hz, 1H, 10-H),
7.85 (d, J = 8.0 Hz, 1H, 3-H), 8.10 (s, 1H, 8-H), 8.43 (s,
A mixture of an appropriate 3-(N-(2-methylquinolin-4-yl) 1H, 14-H), 8.56 (s, 1H, 1-H), 9.01 (d, J = 8.0 Hz, 1H, 4-H);
amino)-9-ethyl-9H-carbazole (7, 1 mmol) and benzoic MS: m/z (%) 583 (M+, 100); Anal. Calcd. for:
acid or toluic acid (1.5 mmol) was added to poly- C41H33N3O: C, 84.36; H, 5.70; N, 7.20%. Found: C,
phosphoric acid (1 g of P2O5 and 0.5 mL of H3PO4) and 84.32; H, 5.75; N, 7.27%.
heated at 160
C for 5 h. After the completion of the reac-
tion, the mixture was poured onto crushed ice and neu-
tralized with saturated sodium bicarbonate solution to 3 | CONCLUSION
remove the excess of benzoic acid. The crude product
thus obtained was purified by column chromatography To summarize, we synthesized benzo[h]carbazol
over silica gel using petroleum ether: ethyl acetate (95:5) [3,2-b][1,6]naphthyridines (4 and 5) from 2-methyl-
as the eluant to obtain yellow solids of corresponding 4-chloroquinolines with 3-aminocarbazole in the pres-
product 4 or 5. ence of CuI, resulting in intermediates that were then
cyclized using PPA with benzoic acid or p-toluic acid to
obtain linear naphthyridines. This approach has opened
2.3.1 | 12-Benzoyl-9-ethyl-2,6-dimethyl- up a new path for libraries of substituted naphthyridines,
7-phenyl-9H-benzo[h]carbazol[3,2-b][1,6] which might have a wide range of uses in the medical
naphthyridine (4a) arena.

Yellow solid; M.p. 133
C; Yield: 0.277 g (50%); IR ACKNOWLEDGMENTS

(KBr, cm1): 2928, 1641, 1600; 1H NMR (500 MHz, We would like to acknowledge the Indian Institute of
CDCl3) (ppm) δ: 1.62 (t, J = 7.5 Hz, 3H, 9-CH2CH3), Technology Madras, Chennai and Indian Institute of
2.53 (s, 3H, 6-CH3), 2.86 (s, 3H, 2-CH3), 4.65 (q, Science, Bangalore for NMR, and the Indian Institute of
J = 7.5 Hz, 2H, 9-CH2CH3), 6.56 (d, J = 2.0 Hz, 1H, Chemical Technology, Hyderabad for mass
13-H), 6.88 (t, J = 8.0 Hz, 2H, 30 & 50 - H), 7.19 (t, spectral data.
J = 8.0 Hz, 1H, 40 -H), 7.39 (d, J = 8.0 Hz, 2H, 20 - & 60 -
H), 7.48 (t, J = 8.0 Hz, 2H, 300 & 500 -H), 7.57 (d, CONFLICT OF INTEREST
J = 8.0 Hz, 1H, 10-H), 7.62–7.65 (m, 5H, 3-, 11-, 200 -, There are no conflicts to declare.
400 - & 600 -H), 8.14 (s, 1H, 8-H), 8.49 (s, 1H, 14-H), 8.58
(s, 1H, 1-H), 8.98 (d, J = 8.0 Hz, 1H, 4-H);13C NMR DA TA AVAI LA BI LI TY S T ATE ME NT
(125 MHz, CDCl3) (ppm) δ: 14.47, 21.86, 29.69, 38.18, The data that support the findings of this study are
108.87, 115.13, 123.07, 123.78, 124.05, 125.75, 128.17, openly available in manuscript at https://www.res-
128.27, 128.34, 128.61, 129.03, 129.24, 129.70, 130.43, earchgate.net/search.Search.html?type=researcher&query=.
131.98, 132.01, 133.36, 134.28, 138.83, 139.30, 140.50,
144.09, 146.74, 148.03, 151.10, 154.33, 196.51; MS: m/z
(%) 555 (M+, 100); Anal. Calcd. for: C39H29N3O: C, ORCID
84.30; H, 5.26; N, 7.56%. Found: C, 84.34; H, Rajendra Prasad Karnam Jayarampillai https://orcid.
5.28; N, 7.57%. org/0000-0002-0647-0332

RE FER EN CES
2.3.2 | 2,6-Dimethyl-9-ethyl-7-p-tolyl- [1] H. A. Younus, M. Al-Rashida, A. Hameed, M. Uroos, U. Salar,
12-toloyl-9H-benzo[h]carbazol[3,2-b][1,6] S. Rana, K. M. Khan, Expert Opin. Ther. Pat. 2021, 31, 267.
[2] M. S. T. A. Azeeze, S. B. Santhosh, M. S. Manjari, S. N.
naphthyridine (5a)
Meyyanathan, Curr. Drug Targets 2021, 22, 1357.
[3] F. Ballesteros, S. Dunivan, K. U. Lao, J. Chem. Phys. 2021, 154,
Yellow solid; M.p. 156
C; Yield: 0.378 g (65%); IR (KBr, 154104.
cm1): 2930, 1640, 1589; 1H NMR (500 MHz, CDCl3) [4] M. Shankar, A. Saha, S. Sau, A. Ghosh, V. Gandon, A. K.
(ppm) δ: 1.62 (t, J = 7.0 Hz, 3H, 9-CH2CH3), 2.00 (s, 3H, Sahoo, Chem. Sci. 2021, 12, 6393.
EZHUMALAI ET AL. 1197

[5] J. Oh, H. H. Lee, Y. Jeong, S. Yoon, H.-J. An, M. Baek, D. K. [13] (a) K. Prabha, K. J. Rajendra Prasad, J. Adv. Res 2015, 6, 631.
Kim, S. Lee, J. Mol. Sci. 2021, 22, 9067. (b) K. Prabha, K. J. R. Prasad, Med. Chem. Commun 2013, 4, 340.
[6] M. Neetha, S. Saranya, N. Ann Harry, G. Anilkumar, Che- [14] M.-Y. Chang, Y.-S. Wu, H.-Y. Chen, Org. Lett. 2018, 20, 1824.
mistrySelect 2020, 5, 736. [15] E. Yamuna, M. Zeller, K. J. Rajendra Prasad, Tetrahedron Lett.
[7] M. Lavanya, C. Lin, J. Mao, D. Thirumalai, S. Reddy Aabaka, 2012, 53, 1514.
X. Yang, J. Mao, Z. Huang, J. Zhao, Top Curr. Chem. 2021, [16] M. Manoj, K. J. Rajendra Prasad, J. Heterocycl. Chem. 2013, 50, 5.
379, 13. [17] (a) V. Gaddam, S. Ramesh, R. Nagarajan, Tetrahedron 2010,
[8] R. A. Kardile, A. P. Sarkate, A. S. Borude, R. S. Mane, D. K. 66, 4218. (b) K. Thirumurthy, G. Thirunarayanan, Arab.
Lokwani, S. V. Tiwari, R. Azad, P. V. L. S. Bur, S. R. Thopate, J. Chem 2018, 11, 443.
Bioorg. Chem. 2021, 115, 105174. [18] Apex2 v2013.4-1 (Bruker), Bruker Advanced X-ray Solutions,
[9] C. Shubhranshu Shekhar, J. Subhrakant, S. Dipak Kumar, S. Bruker AXS Inc., Madison, Wisconsin, USA 2013.
Shamasoddin, K. K. Rajiv, D. Ambuj, G. Konkallu Hanumae, [19] (a) SHELXTL(Version 6.14) (2000-2003) Bruker Advanced
S. B. Himansu, ACS Omega 2021, 6(29), 19304. X-ray Solutions, Bruker AXS. Inc., Madison, Wisconsin: USA.
[10] (a) H. Ban, M. Muraoka, N. Ohashi, Tetrahedron Lett 2003, 44, (b) G. M. Sheldrick, Acta Cryst. 2008, A64, 112.
6021. (b) K. N. Vennila, K. Prabha, D. Sunny, S. Madhuri, [20] (a) G. M. Sheldrick, (2018). University of Gottingen, Germany
K. P. Elango, Med. Chem. Res 2019, 28, 1298. (c) P. (b) G. M. Sheldrick, Acta Cryst. 2015, C71, 3.
Kolandaivel, S. Rajendran, R. P. K. Jayarampillai, J. Heterocycl.
Chem. 2021, 58, 1809.
[11] (a) J. Li, Y. Fu, C. Qin, Y. Yu, H. Li, W. Wang, Org. Biomol. SU PP O R TI N G I N F O RMA TI O N
Chem 2017, 15, 6474. (b) E. L. Smith, A. P. Abbott, K. S. Ryder, Additional supporting information may be found in the
Chem. Rev 2014, 114, 11060. (c) H.-C. Hu, Y.-H. Liu, B.-L. Li,
online version of the article at the publisher's website.
Z.-S. Cui, Z.-H. Zhang, RSC Adv 2015, 5, 7720. (d) N. Azizi,
M. S. Haghayegh, ChemistrySelect 2017, 2(28), 8870.
[12] (a) M. Manoj, K. J. Rajendra Prasad, J. Chem. Res. 2009, (8), How to cite this article: Y. Ezhumalai,
485. (b) M. Manoj, K. J. R. Prasad, J. Chem. Res 2009, (9), 713.
P. Kumaresan, Z. Matthias, R. P. Karnam
(c) M. Manoj, K. J. R. Prasad, Synth. Commun 2010, 40, 3290.
(d) M. Manoj, K. J. R. Prasad, Synth. Commun 2012, 42, 434. e
Jayarampillai, J. Heterocycl. Chem. 2022, 59(7),
C. Masdeu, M. Fuertes, M.-E. Endika, A. Selas, G. Rubiales, F. 1191. https://doi.org/10.1002/jhet.4459
Palacios, C. Alonso, Molecules 2020, 25, 3508.