Synthesis of N-{5-Oxo-2-thioxo(2,5-dithioxo)hexahydroimidazo-[4,5-d]imidazol-1(2H)-yl}formamides

Galina A. Gazieva; Tatyana B. Karpova; Tatyana V. Nechaeva; Yulia V. Nelyubina; Igor E. Zanin; Angelina N. Kravchenko

doi:10.1055/s-0036-1588388

Synlett, Inhaltsverzeichnis

Synlett 2017; 28(07): 858-862
DOI: 10.1055/s-0036-1588388

letter

Synthesis of N-{5-Oxo-2-thioxo(2,5-dithioxo)hexahydroimidazo-[4,5-d]imidazol-1(2H)-yl}formamides

Galina A. Gazieva*

^aN.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prosp. 47, 119991 Moscow, Russian Federation eMail: gaz@ioc.ac.ru

,

Tatyana B. Karpova

^aN.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prosp. 47, 119991 Moscow, Russian Federation eMail: gaz@ioc.ac.ru

,

Tatyana V. Nechaeva

^aN.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prosp. 47, 119991 Moscow, Russian Federation eMail: gaz@ioc.ac.ru

^bD. Mendeleev University of Chemical Technology of Russia, Miusskaya Sq. 9, 125047 Moscow, Russian Federation

,

Yulia V. Nelyubina*

^cA.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova Str. 28, 119991 Moscow, Russian Federation eMail: unelya@xrlab.ineos.ac.ru

,

Igor E. Zanin

^dVoronezh State University, Universitetskaya Sq. 1, 394000 Voronezh, Russian Federation

,

Angelina N. Kravchenko

^aN.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prosp. 47, 119991 Moscow, Russian Federation eMail: gaz@ioc.ac.ru

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

Abstract

A synthetic route to novel N-{5-oxo-2-thioxo(2,5-dithioxo)hexahydroimidazo[4,5-d]imidazol-1(2H)-yl}formamides, by a tandem N-formylation and ring-contraction reaction of 5,7-disubstituted 3-thioxoperhydroimidazo[4,5-e]-1,2,4-triazine-6-ones(thiones) with formic acid, has been developed.

Key words

N-heterocycles - thioanalogues of glycolurils - formylation - ring contraction - tandem reaction

Volltext

Referenzen

References and Notes

1a Mashkovskii MD. Lekarstvennye sredstva [Drugs]. Vol. 1. Novaya Volna; Moscow: 2012: 89
1b Kravchenko AN, Baranov VV, Anikina LV, Vikharev YB, Bushmarinov IS, Nelyubina YV. Russ. J. Bioorg. Chem. 2012; 38: 550 ; Bioorg. Khim. 2012, 38, 621
1c Bakibaev AA, Akhmedzhanov RR, Yagovkin AY, Novozheeva TP, Filimonov VD, Saratikov AS. Pharm. Chem. J. Int. Ed. 1993; 27: 40 ; Khim.-Farm. Zh. 1993, 27, 29
1d Cona MM, Li J, Chen F, Feng Y, Alpizar YA, Vanstapel F, Talavera K, De Witte P, Verbruggen A, Sun Z, Oyen R, Ni Y. Xenobiotica 2013; 43: 730
1e Ryzhkina IS, Kiseleva YV, Murtazina LI, Mishina OA, Timosheva AP, Sergeeva SY, Baranov VV, Kravchenko AN, Konovalov AI. Mendeleev Commun. 2015; 25: 72

2a In S, Kang J. Tetrahedron Lett. 2005; 46: 7165
2b Kang J, In S, Cho S. J. Supramol. Chem. 2007; 19: 243
2c Havel V, Svec J, Wimmerova M, Dusek M, Pojarova M, Sindelar V. Org. Lett. 2011; 13: 4000
2d Toman P, Makrlík E, Vanűra P. Chem. Phys. Lett. 2012; 547: 63
2e Zhang B, Zavalij PY, Isaacs L. Org. Biomol. Chem. 2014; 12: 2413
2f Rezaei-Seresht E, Maleki B, Amiri-Moghaddam Z, Taghizadeh S. Tetrahedron Lett. 2013; 54: 3855
2g Zhang B, Isaacs L. J. Med. Chem. 2014; 57: 9554
2h Yu Y, Li J, Zhang M, Cao L, Isaacs L. Chem. Commun. 2015; 51: 3762
2i Yawer MA, Havel V, Sindelar V. Angew. Chem. Int. Ed. 2015; 54: 276

3a Cow C, Valentini D, Harrison P. Can. J. Chem. 1997; 75: 884
3b Sun S, Edwards L, Harrison P. J. Chem. Soc., Perkin Trans. 1 1998; 437
3c Rahimizadeh M, Kam K, Jenkins SI, McDonald RS, Harrison PH. M. Can. J. Chem. 2002; 80: 517

4 Pryor KE, Rebek JJr. Org. Lett. 1999; 1: 39

5a Stancl M, Hodan M, Sindelar V. Org. Lett. 2009; 11: 4184
5b Ma D, Gargulakova Z, Zavalij PY, Sindelar V, Isaacs L. J. Org. Chem. 2010; 75: 2934
5c Stancl M, Gargulakova Z, Sindelar V. J. Org. Chem. 2012; 77: 10945
5d Cao L.-P, Meng X.-G, Gao M, She N.-F, Wu A.-X. Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 2008; 64: o69
5e She N.-F, Gao M, Meng X.-G, Yang G.-F, Elemans JA. A. W, Wu A.-X, Isaacs L. J. Am. Chem. Soc. 2009; 131: 11695
5f Wang J, Xiang J, Wu A.-X, Meng X.-G. Cryst. Eng. Commun. 2013; 15: 10079
5g Cotelle Y, Hardouin-Lerouge M, Legoupy S, Alvque O, Levillain E, Hudhomme P. Beilstein J. Org. Chem. 2015; 11: 1023
5h Kovalenko EA, Samsonenko DG, Naumov DY, Fedin VP. J. Struct. Chem. 2014; 55: 1448

6a Cow CN, Harrison PH. M. J. Org. Chem. 1997; 62: 8834
6b Kam K, Rahimizadeh M, McDonald RS, Harrison PH. M, Chen H, Jenkins SI, Pedrech A. Can. J. Chem. 2005; 83: 1253
6c Chen H, Harrison PH. M. Can. J. Chem. 2002; 80: 601
6d Bain AD, Chen H, Harrison PH. M. Can. J. Chem. 2006; 84: 421

7 Khaksar S, Vahdat SM, Tajbakhsh M, Jahani F, Heydari A. Tetrahedron Lett. 2010; 51: 6388
8 Cao L, Ding J, Yin G, Gao M, Li Y, Wu A. Synlett 2009; 1445
9 Singh M, Solel E, Keinan E, Reany O. Chem. Eur. J. 2015; 21: 536
10 Gazieva GA, Vikharev YB, Anikina LV, Karpova TB, Kravchenko AN, Permyakov EA, Svitanko IV. Mendeleev Commun. 2013; 23: 202
11 Baranov VV, Gazieva GA, Nelyubina YV, Kravchenko AN, Makhova NN. Russ. J. Org. Chem. 2011; 47: 1564 ; Zh. Org. Khim. 2011, 47, 1535
12 Gazieva GA, Lada V, Anikina SA, Pukhov TB, Karpova YV, Nelyubina YV, Kravchenko AN. Mol. Diversity 2016; 837
13 Singh M, Parvari G, Botoshansky M, Keinan E, Reany O. Eur. J. Org. Chem. 2014; 933

14a Gazieva GA, Poluboyarov PA, Popov LD, Kolotyrkina NG, Kravchenko AN, Makhova NN. Synthesis 2012; 44: 3366
14b Gazieva GA, Karpova TB, Popov LD, Nelyubina YV, Kravchenko AN. J. Heterocycl. Chem. 2015; 52: 1390
14c Kravchenko AN, Gazieva GA, Vasilevsky SV, Belyakov PA, Nelyubina YV. Mendeleev Commun. 2012; 22: 299
14d Gazieva GA, Kravchenko AN. J. Heterocycl. Chem. 2015; 52: 1858

15a Nagy J, Horváth A, Szöllösy Á, Nyitrai J. Eur. J. Org. Chem. 1999; 685
15b Yoneda F, Sakuma Y, Ueno M, Nishigaki S. Chem. Pharm. Bull. 1973; 21: 926

16 Schwan TJ. J. Heterocycl. Chem. 1983; 20: 547
17 Rees CW, Sale AA. J. Chem. Soc., Perkin Trans. 1 1973; 545
18 Lobanov PS, Safarova LA, Potekin AA. Chem. Heterocycl. Compd. 1991; 27: 1120 ; Khim. Geterotsikl. Soedin. 1991, 1392
19 Wojtowicz-Rajchel H, Szczepkowska-Sztolcman J, Katrusiak A, Golankiewicz K. Tetrahedron 2000; 56: 5909

20a Slouka J, Bekarek V, Nalepa K, Lycka A. Collect. Czech. Commun. 1984; 49: 2628
20b Brown DJ, Sugimoto T. J. Chem. Soc. C 1971; 2616

21a Lee S.-C, Park SB. Chem. Commun. 2007; 3714
21b Torchy S, Barbry D. J. Chem. Res., Synop. 2001; 292

22a Gazieva GA, Poluboyarov PA, Kolotyrkina NG, Lubuzh ED, Kravchenko AN. Mendeleev Commun. 2014; 24: 42
22b Gazieva GA, Vasilevskii SV, Belyakov PA, Nelyubina YV, Lubuzh ED, Kravchenko AN. Mendeleev Commun. 2010; 20: 285

23 Representative Analytical Data 7-Methyl-5-phenyl-3-thioxoperhydroimidazo[4,5-e]-1,2,4-triazin-6-one (1c) White solid; yield 0.537 g (51%); mp 258–260 °С (decomp.). ¹H NMR (300 MHz, DMSO-d ₆): δ = 2.73 (s, 3 H, Me), 5.02 (d, J = 8.5 Hz, 1 H, CH), 5.45–5.48 (dd, J = 8.5, 1.9 Hz, 1 H, CH), 5.86 (br s, 1 H, N(1)H), 7.13 (t, J = 7.2 Hz, 1 H, p-PhH), 7.35 (t, J = 7.8 Hz, 2 H, m-PhH), 7.48 (d, J = 8.1 Hz, 2 H, o-PhH), 8.62 (s, 1 H, N(4)H), 9.52 (s, 1 H, N(2)H). ¹³C NMR (75 MHz, DMSO-d ₆): δ = 27.0, 62.1, 69.0, 122.0, 123.9, 128.6, 137.5, 155.8, 184.9. IR: 3208, 2971, 1698, 1595, 1529, 1500, 1477, 1439, 1396, 1303, 1261, 1147, 1120, 746. ESI-HRMS: m/z [M + H] calcd for C₁₁H₁₃N₅OS: 264.0914; found: 264.0907. 7-Methyl-5-phenylperhydroimidazo[4,5-e]-1,2,4-triazin-3,6-dithione (1h) Yellowish solid; yield 0.514 (46%); mp 216–218 °С (decomp.). ¹H NMR (500 MHz, DMSO-d ₆): δ = 3.05 (s, 3 H, Me), 5.32–5.38 (m, 2 H, CH), 5.97 (s, 1 H, N(1)H), 7.30 (d, J = 7.6 Hz, 2 H, o-PhH), 7.33 (t, J = 7.4 Hz, 1 H, p-PhH), 7.42 (t, J = 7.6 Hz, 2 H, m-PhH), 8.70 (s, 1 H, N(4)H), 9.65 (s, 1 H, N(2)H). ¹³C NMR (75 MHz, DMSO-d ₆): δ = 31.1, 66.7, 73.8, 127.2, 128.6, 129.1, 138.2, 181.1, 186.3. IR: 3177, 2959, 1595, 1554, 1500, 1407, 1388, 1335, 1293, 1265, 1213, 1136, 1108, 698. Anal. Calcd for C₁₁H₁₃N₅S₂: C, 47.29; H, 4.69; N, 25.07; S, 22.95. Found: C, 47.32; H, 4.70; N, 25.05; S, 22.91.
24 Synthesis of N-{4,6-Disubstituted 5-Oxo-2-thioxo(2,5-dithioxo)hexahydroimidazo[4,5-d]imidazol-1(2H)-yl}formamides 4a–i; General Procedure To a solution (or suspension) of imidazotriazine 1 (2 mmol) in acetone (22.5 mL) was added 90% formic acid (7.5 mL). The resulting mixture was heated to 55 °C and stirred for 2 h. Then the reaction mixture was cooled to r.t. and allowed to stand for 72 h to attain complete precipitation. The precipitate of compound 4 was ﬁltered, washed with MeOH, and dried. Representative Analytical Data N-{4,6-Dimethyl-5-oxo-2-thioxohexahydroimidazo[4,5-d]-imidazol-1(2H)-yl}formamide (4a) White solid; yield 0.321 g (70%); mp 231–233 °С (decomp.). ¹H NMR (300 MHz, DMSO-d ₆): 70:30 (cis/trans): δ = 2.71 (s, 3 H, NMe), 2.78 (s, 2.1 H, NMe, cis), 2.81 (s, 0.9 H, NMe, trans), 5.34–5.45 (m, 2 H, CHCH), 8.08 (d, J = 10.5 Hz, 0.3 H, HCO, trans), 8.12 (s, 0.7 H, HCO, cis), 9.93 (s, 0.7 H, NH, cis), 9.97 (d, J = 10.5 Hz, 0.3 H, NNH, trans), 10.04 (s, 0.3 H, NH, trans), 10.52 (s, 0.7 H, NNH, cis). ¹³C NMR (75 MHz, DMSO-d ₆): δ = 28.08 (NMe, trans), 28.12 (NMe, cis), 28.9 (NMe, cis), 29.6 (NMe, trans), 68.1 (CH, trans), 68.3 (CH, cis), 75.2 (CH, cis), 76.3 (CH, trans), 157.3 (CO, cis), 157.4 (CO, trans), 159.9 (HNCO, cis), 167.5 (HNCO, trans), 183.4 (CS, cis), 184.4 (CS, trans). IR: 3258, 2944, 2891, 1703, 1680, 1520, 1486, 1419, 1253, 1220, 1047, 754. ESI-HRMS: m/z [M + H] calcd for C₇H₁₁N₅O₂S: 230.0706; found: 230.0700. N-{4,6-Diethyl-5-oxo-2-thioxohexahydroimidazo[4,5-d]-imidazol-1(2H)-yl}formamide (4b) White solid; yield: 0.35 g (68%); mp 228–229 °С (decomp.). ¹H NMR (300 MHz, DMSO-d ₆): 70:30 (cis/trans): δ = 1.02–1.07 (m, 6 H, Me), 3.06–3.41 (m, 4 H, NCH₂), 5.45–5.58 (m, 2 H, CHCH), 8.06 (d, J = 10.3 Hz, 0.3 H, HCO, trans), 8.13 (s, 0.7 H, HCO, cis), 9.94 (d, J = 10.3 Hz, 0.3 H, NNH, trans), 9.95 (s, 0.7 H, NH, cis), 10.05 (s, 0.3 H, NH, trans), 10.56 (s, 0.7 H, NNH, cis). ¹³C NMR (75 MHz, DMSO-d ₆): δ = 12.76 (Me, trans), 12.86 (Me, cis), 12.92 (Me), 36.0 (NCH₂), 36.6 (NCH₂, cis), 37.0 (NCH₂, trans), 66.5 (CH, trans), 66.6 (CH, cis), 73.2 (CH, cis), 74.2 (CH, trans), 156.8 (CO, cis), 157.0 (CO, trans), 160.2 (HNCO, cis), 167.8 (HNCO, trans), 183.7 (CS, cis), 184.6 (CS, trans). IR: 3200, 2988, 2973, 1709, 1677, 1539, 1501, 1470, 1436, 1252, 1229, 1068, 756. ESI-HRMS: m/z [M + H] calcd for C₉H₁₅N₅O₂S: 258.1019; found: 258.1021

Zusatzmaterial

Supporting Information