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Short Note

3-Chloro-5-(4-dodecylthiophen-2-yl)-4H-1,2,6-thiadiazin-4-one

Department of Chemistry, University of Cyprus, P.O. Box 20537, 1678 Nicosia, Cyprus
*
Author to whom correspondence should be addressed.
Molbank 2012, 2012(4), M782; https://doi.org/10.3390/M782
Submission received: 24 September 2012 / Accepted: 12 October 2012 / Published: 16 October 2012

Abstract

:
3-Chloro-5-trifluoromethanesulfonate-4H-1,2,6-thiadiazin-4-one 3 reacts with (4-dodecylthiophen-2-yl)trimethylstannane 5 (1 equiv.) in the presence of Pd(Ph3P)2Cl2 (5 mol%) in benzene at ca. 20 °C for 5 h to give 3-chloro-5-(4-dodecylthien-2-yl)-1,2,6-thiadiazinone 6 in 87% yield.

Graphical Abstract

Surprisingly little has appeared in the literature on nonoxidized 4H-1,2,6-thiadiazines. Monocyclic 3,5-dichloro-4H-1,2,6-thiadiazin-4-one 1 [1] and its 4-dicyanomethylene analogue 2-(3,5-dichloro-4H-1,2,6-thiadiazin-4-ylidene)malononitrile 2 [2,3] have been prepared (Scheme 1), the former in two steps starting from dichloromalononitrile and the latter in one step from tetracyanoethylene (TCNE). Both are useful precursors to several polycyclic 1,2,6-thiadiazine systems [4,5]. For several years now we have been developing the chemistry of both these heterocyclic scaffolds [2,3,4,5,6,7,8,9,10].
Recently, we described the chemoselective Stille reactions of 3-chloro-5-trifluoromethanesulfonate-4H-1,2,6-thiadiazin-4-one 3 which enabled the preparation of unsymmetrical biheteroaryl thiadiazinones and oligomers such as 5,5'-(thiophene-2,5-diyl)bis[3-(thiophen-2-yl)-4H-1,2,6-thiadiazin-4-one] 4 (Scheme 2) [8]. This potentially useful pentamer for optoelectronic materials was unfortunately poorly soluble, as such; the synthesis of an analogue bearing alkyl chains was targeted. To achieve this we required a high yielding synthesis of a alkylthiophene substituted 3-chloro-1,2,6-thiadiazin-4-one.
The reaction of 3-chloro-5-trifluoromethanesulfonate-4H-1,2,6-thiadiazin-4-one 3 with (4-dodecyl-thiophen-2-yl)trimethylstannane 5 (1 equiv.) in the presence of Pd(Ph3P)2Cl2 (5 mol%) proceeded smoothly in benzene (PhH) at ca. 20 °C for 5 h and the desired product 3-chloro-5-(4-dodecylthiophen-2-yl)-4H-1,2,6-thiadiazin-4-one 6 was isolated in 87% yield (Scheme 3).

Experimental

Benzene and acetonitrile was distilled from CaH2, respectively and stored over 4 Å molecular sieves. The reaction mixture and column eluents were monitored by TLC using commercial glass backed thin layer chromatography (TLC) plates (Merck Kieselgel 60 F254). The plates were observed under UV light at 254 and 365 nm. The technique of dry flash chromatography was used using Merck Silica Gel 60 (less than 0.063 mm). Melting points were determined using a PolyTherm-A, Wagner & Munz, Kofler-Hotstage Microscope apparatus. IR spectra were recorded on a Shimadzu FTIR-NIR Prestige-21 spectrometer with Pike Miracle Ge ATR accessory and strong, medium and weak peaks are represented by s, m and w respectively. 1H-NMR spectra were recorded on a BrukerAvance 500 machine at 500 MHz, while 13C-NMR spectra were recorded at 125 MHz. Deuterated chloroform was used for homonuclear lock and the signals are referenced to the deuterated solvent peak. Low resolution (EI) mass spectrum was recorded on a Shimadzu Q2010 GCMS with direct inlet probe. Microanalysis was performed at London Metropolitan University on a Perkin Elmer 2400 Series II CHN Analyzer. 3-Chloro-5-trifluoromethanesulfonate-4H-1,2,6-thiadiazin-4-one 3 [8] and 2-trimethyl-stannyl-4-dodecylthiophene 5 were prepared according to literature procedures [11].
3-Chloro-5-(4-dodecylthiophen-2-yl)-4H-1,2,6-thiadiazin-4-one (6). To a stirred solution of 3-chloro-5-trifluoromethanesulfonate-4H-1,2,6-thiadiazin-4-one 3 (150 mg, 0.506 mmol) in PhH (4 mL) at ca. 20 °C, was added 2-trimethylstannyl-4-dodecylthiophene 5 (210 mg, 0.506 mmol) and Pd(Ph3P)2Cl2 (17.6 mg, 0.025 mmol) and the mixture was stirred until no starting material remained (TLC). The reaction mixture was then adsorbed onto silica and chromatography (hexane/DCM, 7:3) gave the title compound 6 (175.6 mg, 87%) as yellow needles, m.p. 74–76 °C (from pentane/DCM, 0 °C); Rf 0.54 (hexane/DCM, 7:3); (found: C, 57.28; H, 7.00; N, 6.94. C19H27ClN2OS2 requires C, 57.19; H, 6.82; N, 7.02%); λmax(DCM)/nm 278 (log ε 3.60), 370 (3.99), 385 inf (3.91); vmax/cm−1 2949w, 2914s, 2847m, 1645s, 1539w, 1464m, 1422m, 1379w, 1314m, 1285m, 1246w, 1196w, 1180m, 1138m, 1082w, 1020w, 986w, 947w, 872w, 860s, 703s; δH (500 MHz; CDCl3) 8.11 (1H, d, J 1.0 Hz, thienyl H), 7.29 (1H, s, thienyl H), 2.64 (2H, t, J 7.8 Hz), 1.31–1.25 (19H, m), 0.88 (3H, t, J 7.0 Hz, CH3); δC (125 MHz; CDCl3) one carbon (t) resonance missing 159.4 (s), 152.9 (s), 150.9 (s), 144.7 (s), 135.6 (s), 134.6 (d), 129.8 (d), 31.9 (t), 30.4 (t), 30.3 (t), 29.7 (t), 29.6 (t), 29.5 (t), 29.4 (t), 29.3 (t), 29.2 (t), 22.7 (t), 14.1 (q, CH3); m/z (EI) 400 (M++1, 10%), 398 (M+-1, 24), 365 (4), 309 (3), 276 (3), 257 (5), 246 (42), 244 (100), 155 (6), 122 (30), 97 (12), 93 (10), 55 (10).

Supplementary materials

Supplementary File 1Supplementary File 2Supplementary File 3

Acknowledgements

The authors wish to thank the Cyprus Research Promotion Foundation [grant nos. ΠENEK, ENIΣX/0504/08 and NEKYP/0308/02] for financial support. Furthermore, we wish to thank the following organizations in Cyprus for generous donations of chemicals and glassware: the State General Laboratory, the Agricultural Research Institute, the Ministry of Agriculture, Biotronics Ltd and Medochemie Ltd. Finally, we thank the A. G. Leventis Foundation for helping to establish the NMR facility in the University of Cyprus.

References and Notes

  1. Geevers, J.; Trompen, W.P. Synthesis and Reactions of 3,5-Dichloro-4H-1,2,6-Thiadiazin-4-one. Recl. Trav. Chim. Pays-Bas 1974, 93, 270–272. [Google Scholar] [CrossRef]
  2. Koutentis, P.A.; Rees, C.W.; White, A.J.P.; Williams, D.J. Reaction of tetracyanoethylene with SCl2; new molecular rearrangements. J. Chem. Soc. Chem. Commun. 2000, 303–304. [Google Scholar] [CrossRef]
  3. Koutentis, P.A.; Rees, C.W. Reaction of tetracyanoethylene with SCl2; new molecular rearrangements. J. Chem. Soc. Perkin Trans. 1 2000, 1089–1094. [Google Scholar] [CrossRef]
  4. Koutentis, P.A.; Rees, C.W. Cyclisation chemistry of 4H-1,2,6-thiadiazines. J. Chem. Soc. Perkin Trans. 1 2000, 2601–2607. [Google Scholar] [CrossRef]
  5. Kalogirou, A.S.; Koutentis, P.A.; Rikkou, M.D. The synthesis of pyrrolo[2,3-c][1,2,6]thiadiazine-5-carbonitriles from (4H-1,2,6-thiadiazin-4-ylidene)malononitriles. Tetrahedron 2010, 66, 1817–1820. [Google Scholar] [CrossRef]
  6. Koutentis, P.A.; Rees, C.W. Chemistry of 4-dicyanomethyleno-1,2,6-thiadiazines. J. Chem. Soc. Perkin Trans. 1 2000, 1081–1088. [Google Scholar] [CrossRef]
  7. Ioannidou, H.A.; Kizas, C.; Koutentis, P.A. Palladium Catalyzed C-C Coupling Reactions of 3,5-Dichloro-4H-1,2,6-thiadiazin-4-one. Org. Lett. 2011, 13, 3466–3469. [Google Scholar] [CrossRef] [PubMed]
  8. Ioannidou, H.A.; Kizas, C.; Koutentis, P.A. Selective Stille Coupling Reactions of 3-Chloro-5-halo(pseudohalo)-4H-1,2,6-thiadiazin-4-ones. Org. Lett. 2011, 13, 5886–5889. [Google Scholar] [CrossRef] [PubMed]
  9. Ioannidou, H.A.; Koutentis, P.A. Modification of C-4 Position of 3,5-Disubstituted 4H-1,2,6-Thiadiazin-4-ones. Tetrahedron 2012, 68, 2590–2597. [Google Scholar] [CrossRef]
  10. Ioannidou, H.A.; Koutentis, P.A. Synthesis of Asymmetric 3,5-Diaryl-4H-1,2,6-Thiadiazin-4-ones via Suzuki-Miyaura and Stille Coupling Reactions. Tetrahedron 2012, 68, 7380–7385. [Google Scholar] [CrossRef]
  11. Mishra, S.P.; Palai, A.K.; Srivastava, R.; Kamalasanan, M.N.; Patri, M. Dithieno[3,2-b:2′,3′-d]pyrrole–alkylthiophene–benzo[c][1,2,5]thiadiazole-based highly stable and low band gap polymers for polymer light-emitting diodes. J. Polym. Sci. A Polym. Chem. 2009, 47, 6514–6525. [Google Scholar] [CrossRef]
Scheme 1. Structures of 3,5-dichloro-4H-1,2,6-thiadiazin-4-one 1 and 2-(3,5-dichloro-4H-1,2,6-thiadiazin-4-ylidene)malononitrile 2.
Scheme 1. Structures of 3,5-dichloro-4H-1,2,6-thiadiazin-4-one 1 and 2-(3,5-dichloro-4H-1,2,6-thiadiazin-4-ylidene)malononitrile 2.
Molbank 2012 m782 sch001
Scheme 2. Preparation of 5,5'-(thiophene-2,5-diyl)bis[3-(thiophen-2-yl)-4H-1,2,6-thiadiazin-4-one] 4 from 3-chloro-5-trifluoromethanesulfonate-4H-1,2,6-thiadiazin-4-one 3.
Scheme 2. Preparation of 5,5'-(thiophene-2,5-diyl)bis[3-(thiophen-2-yl)-4H-1,2,6-thiadiazin-4-one] 4 from 3-chloro-5-trifluoromethanesulfonate-4H-1,2,6-thiadiazin-4-one 3.
Molbank 2012 m782 sch002
Scheme 3. Synthesis of 3-chloro-5-(4-dodecylthiophen-2-yl)-4H-1,2,6-thiadiazin-4-one 6.
Scheme 3. Synthesis of 3-chloro-5-(4-dodecylthiophen-2-yl)-4H-1,2,6-thiadiazin-4-one 6.
Molbank 2012 m782 sch003

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MDPI and ACS Style

Ioannidou, H.A.; Koutentis, P.A. 3-Chloro-5-(4-dodecylthiophen-2-yl)-4H-1,2,6-thiadiazin-4-one. Molbank 2012, 2012, M782. https://doi.org/10.3390/M782

AMA Style

Ioannidou HA, Koutentis PA. 3-Chloro-5-(4-dodecylthiophen-2-yl)-4H-1,2,6-thiadiazin-4-one. Molbank. 2012; 2012(4):M782. https://doi.org/10.3390/M782

Chicago/Turabian Style

Ioannidou, Heraklidia A., and Panayiotis A. Koutentis. 2012. "3-Chloro-5-(4-dodecylthiophen-2-yl)-4H-1,2,6-thiadiazin-4-one" Molbank 2012, no. 4: M782. https://doi.org/10.3390/M782

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