Synthesis and characterization of novel N-, S-, O-substituted P-chloranil derivatives

Article abstract of DOI:10.1080/00397911.2013.865059

A series of novel N-, S-, and O-substituted p-chloranil derivatives were synthesized from the reactions of p-chloranil (1) and related nucleophiles in sodium carbonate (Na₂CO₃) solution of acetonitrile or in chloroform with Et₃N. The structures of novel compounds were characterized by using microanalysis, Fourier transform-infrared, ¹H NMR, ¹³C NMR, and mass spectrometry.

Full text of DOI:10.1080/00397911.2013.865059

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Synthesis and Characterization of
Novel N-, S-, O-Substituted P-Chloranil
Derivatives
Cemil Ibis a , Sibel Sahinler Ayla a , Yagmur Dogan a & Mesut Ozen a
a Faculty of Engineering, Department of Chemistry , Istanbul
University , Avcilar , Istanbul , Turkey
Accepted author version posted online: 10 Feb 2014.Published
online: 14 May 2014.
To cite this article: Cemil Ibis , Sibel Sahinler Ayla , Yagmur Dogan & Mesut Ozen (2014) Synthesis and
Characterization of Novel N-, S-, O-Substituted P-Chloranil Derivatives, Synthetic Communications:
An International Journal for Rapid Communication of Synthetic Organic Chemistry, 44:11, 1614-1618,
DOI: 10.1080/00397911.2013.865059
To link to this article: http://dx.doi.org/10.1080/00397911.2013.865059
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Synthetic Communications1, 44: 1614–1618, 2014
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397911.2013.865059
SYNTHESIS AND CHARACTERIZATION OF NOVEL
N-, S-, O-SUBSTITUTED P-CHLORANIL DERIVATIVES
Cemil Ibis, Sibel Sahinler Ayla, Yagmur Dogan, and
Mesut Ozen
Faculty of Engineering, Department of Chemistry, Istanbul University,
Avcilar, Istanbul, Turkey
GRAPHICAL ABSTRACT
Abstract A series of novel N-, S-, and O-substituted p-chloranil derivatives were synthesized
from the reactions of p-chloranil (1) and related nucleophiles in sodium carbonate
(Na2CO3) solution of acetonitrile or in chloroform with Et3N. The structures of novel
compounds were characterized by using microanalysis, Fourier transform–infrared,
1H NMR, 13C NMR, and mass spectrometry.
Keywords Amine; p-chloranil; piperazine; thiol
INTRODUCTION
Many applications of quinone compounds can be found in synthetic organic
chemistry.[1–3] Growing attention has been given to the quinone moiety because of
important biologic activity properties such as anticoagulant,[4] antitumor,[5,6]
and anticancer[7] activities. Another application area for p-chloranil derivatives is
acceptors in charge-transfer complexes.[8]
Received September 25, 2013.
Address correspondence to Cemil Ibis, Istanbul University, Faculty of Engineering, Department of
Chemistry, 34320, Avcilar, Istanbul, Turkey. E-mail: ibiscml@istanbul.edu.tr
1614

N-, S-, O-SUBSTITUTED P-CHLORANIL DERIVATIVES
1615
A large number of chemical derivatives with 1,4-naphthoquinone[9,10] and
benzoquinone[11] have been synthesized by our group before. As a continuation of
the synthesis of interesting cyclic thio(crown)ether structures, herein we report novel
intermolecular compounds with diquinone moiety. The aims of this study are the
synthesis of the novel benzoquinone compounds and characterization of them with
spectral methods.
RESULTS AND DISCUSSION
In the formation of substituted quinone compounds, the nucleophiles contain-
ing sulfur or nitrogen atom attack the quinone structure and the addition reaction
occurs.[12,13] Bis-, tris-, or tetrakis-substituted quinone adducts can be obtained in
forward steps depending on the nucleophile structure.[14]
The novel ethoxy and tris(thio)substituted benzoquinone derivatives 3a and 3b
were obtained by the reaction of p-chloranil 1 and 1-octanethiol (2a) and 2-ethylhex-
anethiol (2b) in ethanol with sodium carbonate (Na2CO3) at room temperature
(Scheme 1). In this reaction ethanol behaved as a nucleophile and attacked the
p-chloranile to give the addition reaction in the minority thiol nucleophile. These
compounds were obtained as dark brown oils. In the 13C NMR spectra of compound
3a two carbonyl signals were seen at 173.64 and 177.69 as expected. The molecular
ion peak of compound 3b was identified at m=z (%) 585 (100) in the positive ion
mode for electrospray ionization (ESI) technique.
Compounds 4e and 5e were synthesized by the reaction of p-chloranil (1) with
2 molar equivalents of 4-chlorobenzyl mercaptan (2e) in ethanol with sodium
Scheme 1. Synthetic pathway of novel substituted chloranile compounds.

1616
C. IBIS ET AL.
carbonate (Na2CO3) at room temperature. In the 13C NMR spectra of 2,6-thiosub-
stituted compound 4e two carbonyl carbon signals were observed at 173.76 and
=
177.35 (C O) ppm. The mass spectra of compound 5e in the negative ion mode
of ESI technique confirmed the proposed structure; the deprotonated molecular
ion peak was identified at m=z (%) 734 (100).
The tetrakis(thio)-substituted compounds 5f and 5g were obtained by the
reactions of p-chloranil (1) and related thiol nucleophiles 2f and 2g as black and
orange powders, respectively. The 13C NMR spectra of these compounds gave only
one carbonyl signal at 175.33 and 171.8 ppm because of the symmetric structure of
the quinone moiety. See Scheme 1.
The tris(thio)substituted novel benzoquinone derivatives 6b, 6c, and 6d were
achieved by the reactions of p-chloranil 1 and different molar equivalent related
thiols 2b, 2c, and 2d at room temperature. The infrared (IR) spectra of
compound 6b showed characteristic aliphatic bands (-CH) at 2959, 2928, 2872,
and 2858 cmꢀ1 and a carbonyl band (C O) at 1671 cmꢀ1. The 13C NMR spectra
=
of compound 6c gave carbonyl signals at 170.24 and 174.25 ppm. The molecular
ion peak of compound 6d was identified at m=z 364 in the negative ion mode for
ESI technique.
The 2,5 N,N-substituted benzoquinone derivative 8h was synthesized by the
reaction of p-chloranil 1 and 5-amino-2-methoxypiridine (7h) in chloroform with
triethylamine at room temperature. The IR spectra of compound 8h showed charac-
teristic amine band (-NH) at 3291 cmꢀ1. The reaction of p-chloranil 1 and B-alanine
methyl ester hydrochloride (7i) in methanol with triethylamine at rt gave compound
9i. The solvent methanol behaved as a nucleophile. The mass spectra of compound 9i
in the negative ion mode of ESI technique confirmed the proposed structure; the
deprotonated molecular ion peak was identified at m=z (%) 377 (100).
The reactions of p-chloranil 1 with different molar equivalents of 1,4-butane-
dithiol (10) in chloroform with triethylamine at rt gave novel and interesting cyclic
colored thio(crown)ethers 11 and 12. The interesting cyclic compounds were
obtained as thermodynamic products.[15] The 13C NMR spectra of compound 11
and 12 gave only one carbonyl signal at 177.29 and 178.10 because of the symmetric
structures. The mass spectra of compound 12 in the negative ion mode of ESI
technique confirmed the proposed structure; the deprotonated molecular ion peak
was identified at m=z (%) 589 (100).
The novel piperazine substituted benzoquinone derivative 14 was synthesized
by the reaction of p-chloranil 1 and 1-(4-nitrophenyl)piperazine (13) in chloroform
with triethylamine at rt. The 13C NMR spectra of compound 14 gave carbonyl
signals at 176.10 and 177.32 ppm.
The tetrakis(thio)-substituted benzoquinone derivatives 16a and 16b were
syntesized by the substitution of thiol compound with one chlorine atom in
tris(thio)-substituted compounds. The compound 16a was obtained by the reaction
of compound 6c and 4-chlorobenzylmercaptan (15e) in chloroform with triethyla-
mine at rt. The compound 16b was obtained by the reaction of compound 6c and
4-tert-butylthiophenol (15f) in chloroform with triethylamine at rt. The mass spectra
of compounds 16a and 16b in the positive ion mode of ESI technique confirmed the
proposed structure; the protonated molecular ion peaks were identified at m=z (%)
488 (100) and m=z (%) 495 (100), respectively.

N-, S-, O-SUBSTITUTED P-CHLORANIL DERIVATIVES
1617
EXPERIMENTAL
Synthesis of Cyclic (Thio)crown Ether Compound (12)
Compound 12 was synthesized by the reaction of 1 (p-chloranil (1) (0.5 g,
2.034 mmol) with 1,4-butanedithiol (10) (0.250 g, 2.045 mmol) in chloroform as
solvent (40 mL). Triethylamine (1 mL) was added to the reaction mixture slowly.
Without heating, the mixture was stirred for 12 h. The color of the solution quickly
changed, and the extent of the reaction was monitored by thin-layer chromato-
graphy (TLC). Chloroform (30 mL) was added to the reaction mixture. The organic
layer was separated, washed with water (4 ꢁ 30 mL), and dried with Na2SO4. After
the solvent was evaporated, the residue was purified by column chromatography
on silica gel.
10,11,22,23-Tetra-chloro-2,7,14,19-tetra-tia-tricyclo[18,4,0,08,13]-
tetra-kosa-1(20),8(13),10,22-tetra-en-9,12,21,24-tetraone (12)
Brown solid; mp: 128–129 ꢂC; yield: 0.069 g (6%); Rf: 0.42 [CHCl3]. IR (KBr):
n ¼ 2959.25, 2928.02, 2858.68 (C-H), 1655.63 (C O), 1540.43 (C C). 1H NMR
(499.74 MHz, CDCl3): d ¼ 2.89, 2.91, 2.95, 2.97 (m, J ¼ 7.32 Hz, 4H, -S-CH2),
1.89, 1.93, 1.97 (m, 4H, -S-CH2- CH2), 1.40 1.42, 1.43, 1.45 (m, J ¼ 6.83 Hz, 4H
-S-CH2- CH2- CH2). 13C NMR (125.66 MHz, CDCl3): d ¼ 28.34, 28.67, 29.04,
=
=
=
=
=
29.63 (S-CH2- CH2-CH2–CH2-S-), 124.2 ( C-Cl), 153.1 ( C-S), 178.1 ppm (C O);
MS (-ESI): m=z 589 (M); C20H16Cl4O4S4 (M ¼ 590.41 g=mol). Calcd.: C, 40.69;
H, 2.73; S, 21.72. Found: C, 40.50; H, 2.93; S, 24.32.
CONCLUSION
Novel substituted p-chloranil compounds were synthesized from the reactions
of p-chloranil (1) and related nucleophilles in different reaction media. The structures
1
of novel compounds were characterized by using microanalysis, FT-IR, H NMR,
13C NMR, and MS.
FUNDING
We gratefully thank the Research Fund of the University of Istanbul for
financial support of this work.
SUPPLEMENTAL MATERIAL
Supplemental data for this article can be accessed on the publisher’s website.
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