RU2688221C2 - Method of producing 2,7-dicycloalkyl-4,9-dimethyl-2,3a,5a,7,8a,10a-hexaazaperhydropyrenes - Google Patents
Method of producing 2,7-dicycloalkyl-4,9-dimethyl-2,3a,5a,7,8a,10a-hexaazaperhydropyrenes Download PDFInfo
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- RU2688221C2 RU2688221C2 RU2017126017A RU2017126017A RU2688221C2 RU 2688221 C2 RU2688221 C2 RU 2688221C2 RU 2017126017 A RU2017126017 A RU 2017126017A RU 2017126017 A RU2017126017 A RU 2017126017A RU 2688221 C2 RU2688221 C2 RU 2688221C2
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- dimethyl
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- dicycloalkyl
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- tetraazadecalin
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- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- LYGGRLTYCRTJOP-UHFFFAOYSA-N 2,6-dimethyl-1,2,3,4,4a,5,6,7,8,8a-decahydropyrazino[2,3-b]pyrazine Chemical compound N1C(C)CNC2NC(C)CNC21 LYGGRLTYCRTJOP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 claims abstract description 3
- KZOWNALBTMILAP-JBMRGDGGSA-N ancitabine hydrochloride Chemical group Cl.N=C1C=CN2[C@@H]3O[C@H](CO)[C@@H](O)[C@@H]3OC2=N1 KZOWNALBTMILAP-JBMRGDGGSA-N 0.000 claims 5
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 12
- 238000001819 mass spectrum Methods 0.000 description 7
- 238000000074 matrix-assisted laser desorption--ionisation tandem time-of-flight detection Methods 0.000 description 7
- ZPIPUFJBRZFYKJ-UHFFFAOYSA-N C1=NC=C2C=CC3=CN=CC4=CC=C1C2=C34 Chemical compound C1=NC=C2C=CC3=CN=CC4=CC=C1C2=C34 ZPIPUFJBRZFYKJ-UHFFFAOYSA-N 0.000 description 6
- 230000003595 spectral effect Effects 0.000 description 6
- -1 transition metal cations Chemical class 0.000 description 4
- DRVNNGHVOPNCGY-UHFFFAOYSA-N 1,3,5-tricyclopropyl-1,3,5-triazinane Chemical compound C1CC1N1CN(C2CC2)CN(C2CC2)C1 DRVNNGHVOPNCGY-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- HQJLFRMMLKYIJX-UHFFFAOYSA-N 1,2,3,4,4a,5,6,7,8,8a-decahydropyrazino[2,3-b]pyrazine Chemical compound N1CCNC2NCCNC21 HQJLFRMMLKYIJX-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- ZRAFFUHKPRYPBY-UHFFFAOYSA-N 2,3-dihydro-1h-benzo[de]quinoline Chemical compound C1=CC(NCC2)=C3C2=CC=CC3=C1 ZRAFFUHKPRYPBY-UHFFFAOYSA-N 0.000 description 1
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical compound NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 238000003919 heteronuclear multiple bond coherence Methods 0.000 description 1
- 238000005570 heteronuclear single quantum coherence Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000002495 two-dimensional nuclear magnetic resonance spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
Предлагаемое изобретение относится к органической химии, конкретно, к способу получения 2,7-дициклоалкил-4,9-диметил-2,3а,5а,7,8а,10а-гексаазапергидропиренов общей формулы (1):The present invention relates to organic chemistry, specifically, to a method for producing 2,7-dicycloalkyl-4,9-dimethyl-2,3a, 5a, 7,8a, 10a-hexa-zaperhydropyrene of the general formula (1):
Интерес к полициклическим соединениям, в том числе производным пирена, вызван возможностью их использования в качестве эффективных лекарственных препаратов [S. Roknic, L. Glavas-Obrovac, I. Karner, I. Piantanida, M. Zinic, K. Pavelic, Chemotherapy, 2000, 46, 143; A.D. Andricopolo, L.A. Muller, V.C. Filho, G.-N. R.J. Cani, R.A. Yunes, Farmaco, 2000, 55, 319], органических люминофоров [H.E. Katz, J. Johnson, A.J. Lovinger, W. Li, J. Am. Chem. Soc., 2000, 122, 7787], макрокомплексов с катионами переходных металлов [P.J. Stang, D.Н. Cao, S. Saito, and А.М. Arif, J. Am. Chem. Soc., 1995, 117, 6273; P.J. Stang, B. Olenyuk, J. Fan, and A.M. Arif, Organometallics, 1996, 15, 904], а также потенциальных «строительных блоков» в супрамолекулярной химии [V. Balzani, A. Credi, S.J. Langford, F.M. Raymo, J.F. Stoddart, and M. Venturi, J. Am. Chem. Soc., 2000, 122, 3542].Interest in polycyclic compounds, including a derivative of pyrene, is due to the possibility of their use as effective drugs [S. Roknic, L. Glavas-Obrovac, I. Karner, I. Piantanida, M. Zinic, K. Pavelic, Chemotherapy, 2000, 46, 143; A.D. Andricopolo, L.A. Muller, V.C. Filho, G.-N. R.J. Cani, R.A. Yunes, Farmaco, 2000, 55, 319], organic phosphors [H.E. Katz, J. Johnson, A.J. Lovinger, W. Li, J. Am. Chem. Soc., 2000, 122, 7787], macrocomplexes with transition metal cations [P.J. Stang, D.N. Cao, S. Saito, and A.M. Arif, J. Am. Chem. Soc., 1995, 117, 6273; P.J. Stang, B. Olenyuk, J. Fan, and A.M. Arif, Organometallics, 1996, 15, 904], as well as potential “building blocks” in supramolecular chemistry [V. Balzani, A. Credi, S.J. Langford, F.M. Raymo, J.F. Stoddart, and M. Venturi, J. Am. Chem. Soc., 2000, 122, 3542].
Известен способ [A.V. Aksenov, I.V. Borovlev, I.V. Aksenova, S.V. Pisarenko, and D.A. Kovalev. Tetrahedron Lett., 2008, 49, 707] получения 2,7-диазапирена (2) взаимодействием дигидроазафеналена с сим-триазином.The known method [A.V. Aksenov, I.V. Borovlev, I.V. Aksenova, S.V. Pisarenko, and D.A. Kovalev. Tetrahedron Lett., 2008, 49, 707] for preparing 2,7-diazapyrene (2) by reacting dihydroazaphenalene with sym-triazine.
Известный способ не позволяет получать 2,7-дициклоалкил-4,9-диметил-2,3а,5а,7,8а,10а-гексаазапергидропирены общей формулы (1).The known method does not allow to obtain 2,7-dicycloalkyl-4,9-dimethyl-2,3a, 5a, 7,8a, 10a-hexaazaperhydropyrenes of the general formula (1).
Известен способ [М. Antoine, Н. Bernard, N. Kervareca, Н. Handel, J. Chem. Soc., Perkin Trans. 2002, 2, 552] получения стереоизомерных тетраазапергидропиренов (3, 4) реакцией 1,4,5,8-тетраазадекалина с метил акрилатом.The known method [M. Antoine, N. Bernard, N. Kervareca, N. Handel, J. Chem. Soc., Perkin Trans. 2002, 2, 552], to obtain stereoisomeric tetraazaperhydropyrenes (3, 4) by the reaction of 1,4,5,8-tetraazadecalin with methyl acrylate.
Известный способ не позволяет получать 2,7-дициклоалкил-4,9-диметил-2,3а,5а,7,8а,10а-гексаазапергидропирены общей формулы (1).The known method does not allow to obtain 2,7-dicycloalkyl-4,9-dimethyl-2,3a, 5a, 7,8a, 10a-hexaazaperhydropyrenes of the general formula (1).
Известен способ получения [P. Neumann, A. Aumueller, Н. Trauth. US Patent 4,904,779 (1990)] бис(пиперидинил)гексаазапергидропирена (5) трехкомпонентной конденсацией 4-аминопиперидина, параформальдегида и 1,4,5,8-тетраазадекалина в среде этанола в присутствии в качестве катализатора сильнокислого катионита Lewatit.A known method of obtaining [P. Neumann, A. Aumueller, N. Trauth. US Patent 4,904,779 (1990)] bis (piperidinyl) hexa-zaperhydropyrene (5) by three-component condensation of 4-aminopiperidine, paraformaldehyde and 1,4,5,8-tetraazadecalin in ethanol in the presence of Lewatit, a strongly acidic cation exchanger as a catalyst.
Известный способ не позволяет получать 2,7-дициклоалкил-4,9-диметил-2,3а,5а,7,8а,10а-гексаазапергидропирены общей формулы (1).The known method does not allow to obtain 2,7-dicycloalkyl-4,9-dimethyl-2,3a, 5a, 7,8a, 10a-hexaazaperhydropyrenes of the general formula (1).
Известен способ получения [Elena В. Rakhimova, Rinat A. Ismagilov, Ekaterina S. Meshcheryakova, Leonard M. Khalilov, Askhat G. Ibragimov, Usein M. Dzhemilev. Tetrahedron Letters, 2014, 55, 46, 6367-6369.] 2,7-диалкил-2,3a,5a,7,8a,10а-гексаазапергидропиренов (6) взаимодействием N,N-бис(метоксиметил)-N-алкиламинов с 1,4,5,8-тетраазадекалином в присутствии катализатора на основе Sm.A known method of obtaining [Elena B. Rakhimova, Rinat A. Ismagilov, Ekaterina S. Meshcheryakova, Leonard M. Khalilov, Askhat G. Ibragimov, Usein M. Dzhemilev. Tetrahedron Letters, 2014, 55, 46, 6367-6369.] 2,7-dialkyl-2,3a, 5a, 7,8a, 10a-hexa-zaperhydropyrenes (6) by reacting N, N-bis (methoxymethyl) -N-alkylamines with 1,4,5,8-tetraazadekalin in the presence of a catalyst based on Sm.
Известный способ не позволяет получать 2,7-дициклоалкил-4,9-диметил-2,3а,5а,7,8а,10а-гексаазапергидропирены общей формулы (1).The known method does not allow to obtain 2,7-dicycloalkyl-4,9-dimethyl-2,3a, 5a, 7,8a, 10a-hexaazaperhydropyrenes of the general formula (1).
Таким образом, в литературе отсутствуют сведения о получении 2,7-дициклоалкил-4,9-диметил-2,3а,5а,7,8а,10а-гексаазапергидропиренов общей формулы (1).Thus, in the literature there is no information on the preparation of 2,7-dicycloalkyl-4,9-dimethyl-2,3a, 5a, 7,8a, 10a-hexa-zaperhydropyrenes of the general formula (1).
Предлагается новый способ получения 2,7-дициклоалкил-4,9-диметил-2,3а,5а,7,8а,10а-гексаазапергидропиренов общей формулы (1).A new method for the preparation of 2,7-dicycloalkyl-4,9-dimethyl-2,3a, 5a, 7,8a, 10a-hexaazaperhydropyrene of the general formula (1) is proposed.
Сущность способа заключается во взаимодействии 1,3,5-трициклоалкил-1,3,5-триазина общей формулы (RNCH2)3, где R = циклопропил, циклопентил, циклогексил, циклогептил, циклооктил, норборнил, с 2,6-диметил-1,4,5,8-тетраазадекалином в присутствии катализатора NiGl2⋅6H2O, взятых в мольном соотношении 1,3,5-трициклоалкил-1,3,5-триазин : 2,6-диметил-1,4,5,8-тетраазадекалин : NiCl2⋅6H2O = 2:1:(0.03-0.07), предпочтительно 2:1:0.05. Реакционную смесь перемешивают 2.5-3.5 ч при температуре 20°С и атмосферном давлении в среде СН3ОН-Н2О. Выход 2,7-дициклоалкил-4,9-диметил-2,3а,5а,7,8а,10а-гексаазапергидропиренов (1) составляет 68-92%. Реакция протекает по схеме:The essence of the method consists in the interaction of 1,3,5-tricycloalkyl-1,3,5-triazine of the general formula (RNCH 2 ) 3 , where R = cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, with 2,6-dimethyl- 1,4,5,8-tetraazadekalin in the presence of a catalyst NiGl 2 ⋅ 6H 2 O, taken in a molar ratio of 1,3,5-tricycloalkyl-1,3,5-triazine: 2,6-dimethyl-1,4,5 , 8-tetraazadekalin: NiCl 2 ⋅ 6H 2 O = 2: 1: (0.03-0.07), preferably 2: 1: 0.05. The reaction mixture is stirred for 2.5-3.5 hours at a temperature of 20 ° C and atmospheric pressure in an environment of CH 3 OH-H 2 O. The yield of 2,7-dicycloalkyl-4,9-dimethyl-2,3a, 5a, 7,8a, 10a Hexaazaperhydropyrenes (1) is 68-92%. The reaction proceeds according to the scheme:
2,7-Дициклоалкил-4,9-диметил-2,3а,5а,7,8а,10а-гексаазапергидропирены общей формулы (1) образуются только лишь с участием 1,3,5-трициклоалкил-1,3,5-триазинов и 2,6-диметил-1,4,5,8-тетраазадекалина, взятых в мольном соотношении 2:1 (стехиометрические количества). При другом соотношении исходных реагентов снижается выход целевого продукта (1). Без катализатора реакция идет с выходом не более 10%.2,7-Dicycloalkyl-4,9-dimethyl-2,3a, 5a, 7,8a, 10a-hexa-zaperhydropyrenes of general formula (1) are formed only with the participation of 1,3,5-tricycloalkyl-1,3,5-triazines and 2,6-dimethyl-1,4,5,8-tetraazadecalin, taken in a molar ratio of 2: 1 (stoichiometric amounts). With a different ratio of initial reagents, the yield of the target product (1) decreases. Without a catalyst, the reaction proceeds with a yield of no more than 10%.
Проведение указанной реакции в присутствии катализатора NiCl2-6H2O больше 7 мол. % не приводит к существенному увеличению выхода целевого продукта (1). Использование катализатора NiCl2⋅6H2O менее 3 мол. % снижает выход (1), что связано, возможно, со снижением каталитически активных центров в реакционной массе. Реакции проводили при температуре 20°С. При температуре выше 20°С (например, 60°С) увеличиваются энергозатраты, а при температуре ниже 20°С (например, при 0°С) снижается скорость реакции. Опыты проводили в среде СН3ОН-H2O, т.к. в ней хорошо растворяются исходные соединения.Conducting this reaction in the presence of a catalyst NiCl 2 -6H 2 O is more than 7 mol. % does not lead to a significant increase in the yield of the target product (1). The use of catalyst NiCl 2 ⋅ 6H 2 O less than 3 mol. % reduces the yield (1), which is connected, possibly, with a decrease in catalytically active centers in the reaction mass. Reactions were carried out at a temperature of 20 ° C. At temperatures above 20 ° C (for example, 60 ° C), energy consumption increases, and at temperatures below 20 ° C (for example, at 0 ° C), the reaction rate decreases. The experiments were carried out in medium CH 3 OH-H 2 O, since the starting compounds dissolve well in it.
Существенные отличия предлагаемого способа:Significant differences of the proposed method:
В известном способе реакция идет с участием в качестве исходных реагентов N,N-бис(метоксиметил)-N-алкиламина и 1,4,5,8-тетраазадекалина под действием катализатора SmCl3⋅6H2O.In the known method, the reaction proceeds with the participation of N, N-bis (methoxymethyl) -N-alkylamine and 1,4,5,8-tetraazadecalin as the initial reagents under the influence of the catalyst SmCl 3 ⋅ 6H 2 O.
В предлагаемом способе реакция идет с участием в качестве исходных реагентов 1,3,5-трициклоалкил-1,3,5-триазина и 2,6-диметил-1,4,5,8-тетраазадекалина под действием катализатора NiCl2⋅6H2O.In the proposed method, the reaction proceeds with the participation of 1,3,5-tricycloalkyl-1,3,5-triazine and 2,6-dimethyl-1,4,5,8-tetraazadecalin as a reactant under the influence of the catalyst NiCl 2 .6H 2 O.
Предлагаемый способ обладает следующими преимуществами:The proposed method has the following advantages:
В отличие от известных, предлагаемый способ позволяет получать индивидуальные 2,7-дициклоалкил-4,9-диметил-2,3а,5а,7,8а,10а-гексаазапергидропирены общей формулы (1), синтез которых в литературе не описан.In contrast to the known, the proposed method allows to obtain individual 2,7-dicycloalkyl-4,9-dimethyl-2,3a, 5a, 7,8a, 10a-hexa-zaperhydropyrenes of general formula (1), the synthesis of which is not described in the literature.
Способ поясняется примерами:The method is illustrated by examples:
ПРИМЕР 1. Синтез 1,3,5-трициклопропил-1,3,5-триазина : смесь 0.17 г (3 ммоль) циклопропиламина и 0.09 г (3 ммоль) параформа в 10 мл метанола перемешивают 3 ч при 60°С, экстрагируют CHCl3, упаривают и выделяют 1,3,5-трициклопропил-1,3,5-триазин.EXAMPLE 1. Synthesis of 1,3,5-tricyclopropyl-1,3,5-triazine: a mixture of 0.17 g (3 mmol) of cyclopropylamine and 0.09 g (3 mmol) of paraform in 10 ml of methanol is stirred for 3 hours at 60 ° C, extracted with CHCl 3 , evaporated and 1,3,5-tricyclopropyl-1,3,5-triazine is isolated.
ПРИМЕР 2. Синтез 2,6-диметил-1,4,5,8-тетраазадекалина : смесь 15 мл (2 ммоль) 1,2-диаминопропана и 6 мл (1 ммоль) глиоксаля в 10 мл метанола перемешивают 3 ч при 70°С. Образовавшийся осадок отфильтровывают, промывают метанолом и высушивают. Выделяют 2,6-диметил-1,4,5,8-тетраазадекалин.EXAMPLE 2. Synthesis of 2,6-dimethyl-1,4,5,8-tetraazadecalin: a mixture of 15 ml (2 mmol) of 1,2-diaminopropane and 6 ml (1 mmol) of glyoxal in 10 ml of methanol is stirred for 3 hours at 70 ° WITH. The precipitate formed is filtered off, washed with methanol and dried. Allocate 2,6-dimethyl-1,4,5,8-tetraazadekalin.
Пример 3. В круглодонную колбу, установленную на магнитной мешалке, при температуре ~20°С помещают 0.41 г (2 ммоль) 1,3,5-трициклопропил-1,3,5-триазина в 10 мл метанола и 0.007 г (0.05 ммоль) NiCl2⋅6Н2О, затем добавляют 0.17 г (1 ммоль) 2,6-диметил-1,4,5,8-тетраазадекалина. Реакционную смесь перемешивают при температуре ~20°С в течение 3 ч и очищают колоночной хроматографией на SiO2, выделяют 2,7-дициклопропил-4,9-диметил-2,3а,5а,7,8а,10а-гексаазапергидропирен с выходом 79%.Example 3. In a round bottom flask mounted on a magnetic stirrer, at a temperature of ~ 20 ° C, 0.41 g (2 mmol) of 1,3,5-tricyclopropyl-1,3,5-triazine are placed in 10 ml of methanol and 0.007 g (0.05 mmol ) NiCl 2 .6H 2 O, then 0.17 g (1 mmol) of 2,6-dimethyl-1,4,5,8-tetraazadecalin is added. The reaction mixture is stirred at a temperature of ~ 20 ° C for 3 hours and purified by column chromatography on SiO 2 , 2,7-dicyclopropyl-4,9-dimethyl-2,3a, 5a, 7,8a, 10a-hexa-zaperhydropyrene is isolated with the yield 79 %
Другие примеры, подтверждающие способ, приведены в табл. 1.Other examples confirming the method are given in table. one.
Все опыты проводили в среде СН3ОН-H2O при комнатной температуре (~20°С).All experiments were carried out in medium CH 3 OH-H 2 O at room temperature (~ 20 ° C).
Спектральные характеристики 2,7-дициклопропил-4,9-диметил-2,3а,5а,7,8а,10а-гексаазапергидропирена1: (1 Контроль реакции осуществляли методом ТСХ на пластинах Silufol W-254, проявляли парами I2. Для колоночной хроматографии использовали силикагель КСК (100-200 мкм). Масс спектры получены на приборе MALDI TOF/TOF AUTOFLEX III фирмы Bruker. Спектры ЯМР 1D (1Н, 13С) и 2D (COSY, NOESY, HSQC, НМВС) сняты на спектрометре Bruker Avance 400 (100.62 МГц для 13С и 400.13 МГц для 1Н) по стандартным методикам фирмы Bruker, внутренний стандарт Me4Si, растворитель - CDCl3.):The spectral characteristics of 2,7-dicyclopropyl-4,9-dimethyl-2,3a, 5a, 7,8a, 10a-hexa-zaperhydropyrene 1 : ( 1 The reaction was monitored by TLC on Silufol W-254 plates, developed in pairs I 2. For column chromatography used KSK silica gel (100-200 μm). Mass spectra were obtained on a MALDI TOF / TOF AUTOFLEX III instrument from Bruker. The 1D ( 1 H, 13 C) and 2D NMR spectra (COZY, NOESY, HSQC, HMBC) were taken on a Bruker spectrometer Avance 400 (100.62 MHz for 13 C and 400.13 MHz for 1 N) according to standard methods of Bruker, internal standard Me 4 Si, solvent - CDCl 3. ):
Спектр ЯМР 1Н, δ, м.д. (J, Гц): 0.42-0.48 м (8Н, СН2, Н-2', 2'', 3', 3''), 1.03 д (6Н, СН3, Н-11, 12, J=7.5), 2.02 т (2Н, СН2, Н а -5, 10, 2Jab=13), 2.38-2.58 м (2Н, СН2, Hb-5, 10; 6Н, СН, Н-1', 1'', 4, 9, 10b, 10с), 2.89 д (2Н, СН2, Н а -3, 8, 2Jab=12), 2.95 д (2Н, СН2, Н а -1, 6, 2Jab=12), 3.72 д (2Н, СН2, Hb-1, 6, 2Jba=12), 4.07 д (2Н, СН2, Hb-3, 8, 2Jba=12).NMR spectrum 1 H, δ, ppm (J, Hz): 0.42-0.48 m (8H, CH 2 , H-2 ', 2 ", 3', 3"'), 1.03 d (6H, CH 3 , H-11, 12, J = 7.5 ), 2.02 t (2H, CH 2 , H a- 5, 10, 2 J ab = 13), 2.38-2.58 m (2H, CH 2 , H b -5, 10; 6H, CH, H-1 ', 1 ", 4, 9, 10b, 10c), 2.89 d (2H, CH 2 , H a -3, 8, 2 J ab = 12), 2.95 d (2H, CH 2 , H a -1, 6, 2 J ab = 12), 3.72 d (2H, CH 2 , H b -1, 6, 2 J ba = 12), 4.07 d (2H, CH 2 , H b -3, 8, 2 J ba = 12) .
Спектр ЯМР 13С, δ, м.д.: 6.48 и 6.55 (С-2', С-2'', С-3', С-3''), 16.79 (С-11, С-12), 33.38 (С-1', С-1''), 51.60 (С-4, С-9), 56.39 (С-5, С-10), 71.17 (С-3, С-8), 74.40 (С-1, С-6), 82.67 (С-10b, С-10с).An NMR spectrum of 13 C, δ, ppm: 6.48 and 6.55 (C-2 ', C-2 ", C-3', C-3"), 16.79 (C-11, C-12), 33.38 (C-1 ', C-1 "), 51.60 (C-4, C-9), 56.39 (C-5, C-10), 71.17 (C-3, C-8), 74.40 (C -1, C-6), 82.67 (C-10b, C-10s).
Масс-спектр (MALDI TOF/TOF), m/z (Ioтн, %): 333 [М+Н]+(100).Mass spectrum (MALDI TOF / TOF), m / z (I ont ,%): 333 [M + H] + (100).
Спектральные характеристики 2,7-дициклопентил-4,9-диметил-2,3а,5а,7,8а,10а-гексаазапергидропирена:The spectral characteristics of 2,7-dicyclopentyl-4,9-dimethyl-2,3a, 5a, 7,8a, 10a-hexaazaperperidine:
Спектр ЯМР 1Н, δ, м.д. (J, Гц): 1.01 д (6Н, СН3, Н-11, 12, J=7), 1.30-1.40 м (4Н, СН2, Н а -2', 2'', 5', 5''), 1.54-1.62 м (4Н, СН2, Н а -3', 3'', 4', 4''), 1.65-1.73 м (4Н, СН2, Нb-3', 3'', 4', 4''), 1.85-1.92 м (4Н, СН2, Hb-2', 2'', 5', 5''), 1.97 т (2Н, СН2, Н а -5, 10, 2Jab=13), 2.35-2.48 м (2Н, СН2, Hb-5, 10; 4Н, СН, Н-4, 9, 10b, 10с), 2.86 д (2Н, СН2, Н а -3, 8, 2Jab=12.5), 2.94 д (2Н, СН2, H2-1, 6, 2Jab=12.5), 3.32-3.36 м (2H, СН, Н-1', 1''), 3.72 д (2Н, СН2, Hb-1, 6, 2Jba=12.5), 4.11 д (2Н, СН2, Hb-3, 8, 2Jba=12.5).NMR spectrum 1 H, δ, ppm (J, Hz): 1.01 d (6H, CH 3 , H-11, 12, J = 7), 1.30-1.40 m (4H, CH 2 , H a -2 ', 2 ", 5', 5 ''), 1.54-1.62 m (4H, CH 2 , H a- 3', 3 ", 4 ', 4"'), 1.65-1.73 m (4H, CH 2 , H b- 3 ', 3 " , 4 ', 4 ""), 1.85-1.92 m (4H, CH 2 , H b -2', 2 ", 5 ', 5"'), 1.97 t (2H, CH 2 , H a- 5, 10, 2 J ab = 13), 2.35-2.48 m (2H, CH 2 , H b -5, 10; 4H, CH, H-4, 9, 10b, 10s), 2.86 d (2H, CH 2 , H a -3, 8, 2 J ab = 12.5), 2.94 d (2H, CH 2 , H 2 -1, 6, 2 J ab = 12.5), 3.32-3.36 m (2H, CH, H-1 ', 1 ""), 3.72 d (2H, CH 2 , H b -1, 6, 2 J ba = 12.5), 4.11 d (2H, CH 2 , H b -3, 8, 2 J ba = 12.5).
Спектр ЯМР 13С, δ, м.д.: 16.75 (С-11, С-12), 23.93 и 24,00 (С-3', С-3'', С-4', С-4''), 31.26 (С-2', С-2'', С-5', С-5''), 51.33 (С-4, С-9), 56.46 (С-5, С-10), 60.06 (С-1', С-1''), 69.87 (С-3, С-8), 73.41 (С-1, С-6), 82.62 (С-10b, С-10с).NMR spectrum 13 C, δ, ppm: 16.75 (C-11, C-12), 23.93 and 24.00 (C-3 ', C-3 ", C-4', C-4" ), 31.26 (C-2 ', C-2 ", C-5', C-5"), 51.33 (C-4, C-9), 56.46 (C-5, C-10), 60.06 (C-1 ', C-1''), 69.87 (C-3, C-8), 73.41 (C-1, C-6), 82.62 (C-10b, C-10s).
Масс-спектр (MALDI TOF/TOF), m/z (Ioтн, %): 387 [M-H]+ (100).Mass spectrum (MALDI TOF / TOF), m / z (I ref ,%): 387 [MH] + (100).
Спектральные характеристики 2,7-дициклогексил-4,9-диметил-2,3а,5а,7,8а,10а-гексаазапергидропирена:Spectral characteristics of 2,7-dicyclohexyl-4,9-dimethyl-2,3a, 5a, 7,8a, 10a-hexaazaperhydropyrene:
Спектр ЯМР 1Н, δ, м.д. (J, Гц): 1.02 д (6Н, СН3, Н-11, 12, J=7.5), 1.08-1.18 м (6Н, СН2, На-2', 2'', 4', 4'', 6', 6''), 1.24-1.34 м (4Н, СН2, Н а -3', 3'', 5', 5''), 1.62 уш. с (2Н, СН2, Hb-4', 4''), 1.72-1.80 м (4Н, СН2, Hb-3', 3'', 5', 5''), 1.93-2.03 м (6Н, СН2, Н а -5, 10; Hb-2', 2'', 6', 6''), 2.36-2.48 м (2Н, СН2, Hb-5, 10; 4Н, СН, Н-4, 9, 10b, 10с), 2.80-2.86 м (2Н, СН, Н-1', 1''), 2.88 д (2Н, СН2, Н а -3, 8, 2Jab=12.5), 2.96 д (2Н, СН, H a -1, 6, 2Jab=12,5), 3.80 д (2Н, СН2, Hb-1, 6, 2Jba=12.5), 4.19 д (2Н, СН2, Hb-3, 6, 2Jba=12.5).NMR spectrum 1 H, δ, ppm (J, Hz): 1.02 d (6H, CH 3 , H-11, 12, J = 7.5), 1.08-1.18 m (6H, CH 2 , H a -2 ', 2 ", 4', 4 '',6', 6 ''), 1.24-1.34 m (4H, CH 2 , H a- 3 ', 3'',5', 5 ''), 1.62 br. with (2H, CH 2 , H b -4 ', 4 "), 1.72-1.80 m (4H, CH 2 , H b -3', 3", 5 ', 5 "', 1.93-2.03 m (6H, CH 2 , H a- 5, 10; H b -2 ', 2 ", 6', 6"'), 2.36-2.48 m (2H, CH 2 , H b -5, 10; 4H, CH, H-4, 9, 10b, 10s), 2.80-2.86 m (2H, CH, H-1 ', 1 ""), 2.88 d (2H, CH 2 , H a -3, 8, 2 J ab = 12.5), 2.96 d (2H, CH, H a -1, 6, 2 J ab = 12.5), 3.80 d (2H, CH 2 , H b -1, 6, 2 J ba = 12.5), 4.19 d (2H, CH 2 , H b -3, 6, 2 J ba = 12.5).
Спектр ЯМР 13С, δ, м.д.: 16.72 (С-11, С-12), 25.34 и 25.38 (С-3', С-3'', С-5', С-5''), 26.09 (С-4', С-4''), 30.50 и 30.91 (С-2', С-2'', С-6', С-6''), 51.47 (С-4, С-9), 56.44 (С-5, С-10), 57.08 (С-1', С-1''), 61.71 (С-3, С-8), 71.15 (С-1, С-6), 82.84 (С-10b, С-10с).An NMR spectrum of 13 C, δ, ppm: 16.72 (C-11, C-12), 25.34 and 25.38 (C-3 ', C-3 ", C-5', C-5"), 26.09 (C-4 ', C-4 "), 30.50 and 30.91 (C-2', C-2", C-6 ', C-6 "), 51.47 (C-4, C-9 ), 56.44 (C-5, C-10), 57.08 (C-1 ', C-1''), 61.71 (C-3, C-8), 71.15 (C-1, C-6), 82.84 (C-10b, C-10c).
Масс-спектр (MALDI TOF/TOF), m/z (Ioтн, %): 415 [M-H]+(100).Mass spectrum (MALDI TOF / TOF), m / z (I mon ,%): 415 [MH] + (100).
Спектральные характеристики 2,7-дициклогептил-4,9-диметил-2,3а,5а,7,8а,10а-гексаазапергидропирена:Spectral characteristics of 2,7-dicycloheptyl-4,9-dimethyl-2,3a, 5a, 7,8a, 10a-hexaazaperhydropyrene:
Спектр ЯМР 1Н, δ, м.д. (J, Гц): 1.01 д (6Н, СН3, Н-11, 12, J=7.5), 1.35-1.45 м (4Н, СН2, Н а -3', 3'', 6', 6''), 1.47-1.57 м (12Н, СН2, Н-4', 4'', 5', 5''; Н а -2', 2'', 7', 7''), 1.59-1.69 м (4Н, СН2, Hb-3', 3'', 6', 6''), 1.80-1.90 м (4Н, СН2, Hb-2', 2'', 7', 7''), 2.00 т (2Н, СН2, Н a -5, 10, 2Jab=13), 2.37 уш. с (2Н, СН, Hb-10b, 10с), 2.39-2.49 м (2Н, СН, Н-4, 9; 2Н, СН2, Hb-5, 10), 2.81 д (2Н, СН2, Н а -3, 8, 2Jab=12), 2.88 д (2Н, СН2, Н а -1, 6, 2Jab=12), 2.91-2.98 м (2Н, СН, Н-1', 1''), 3.70 д (2Н, СН2, Hb-1, 6, 2Jba=12), 4.07 д (2Н, СН2, Hb-3, 8, 2Jba=12).NMR spectrum 1 H, δ, ppm (J, Hz): 1.01 d (6H, CH 3 , H-11, 12, J = 7.5), 1.35-1.45 m (4H, CH 2 , H a -3 ', 3 ", 6', 6 ''), 1.47-1.57 m (12H, CH 2 , H-4', 4 ", 5 ', 5"'; H a -2 ', 2 ", 7', 7"'), 1.59-1.69 m (4H, CH 2 , H b -3 ', 3 ", 6', 6"), 1.80-1.90 m (4H, CH 2 , H b -2 ', 2 ", 7', 7 ''), 2.00 t (2H, CH 2 , H a- 5, 10, 2 J ab = 13), 2.37 br. s (2H, CH, H b -10b, 10s), 2.39-2.49 m (2H, CH, H-4, 9; 2H, CH 2 , H b -5, 10), 2.81 d (2H, CH 2 , H a- 3, 8, 2 J ab = 12), 2.88 d (2H, CH 2 , H a -1, 6, 2 J ab = 12), 2.91-2.98 m (2H, CH, H-1 ', 1 ''), 3.70 d (2H, CH 2 , H b -1, 6, 2 J ba = 12), 4.07 d (2H, CH 2 , H b -3, 8, 2 J ba = 12).
Спектр ЯМР 13С, δ, м.д.: 16.74 (С-11, С-12), 24.74 и 24.81 (С-3', С-3'', С-6', С-6''), 28.44 (С-4', С-4'', С-5', С-5''), 31.00 и 31.51 (С-2', С-2'', С-7', С-7''), 51.61 (С-4, С-9), 56.65 (С-5, С-10), 60.15 (С-1', С-1''), 68.45 (С-3, С-8), 71.58 (С-1, С-6), 82.67 (С-10b, С-10с).An NMR spectrum of 13 C, δ, ppm: 16.74 (C-11, C-12), 24.74 and 24.81 (C-3 ', C-3 ", C-6', C-6"), 28.44 (C-4 ', C-4 ", C-5', C-5"), 31.00 and 31.51 (C-2 ', C-2 ", C-7', C-7" ), 51.61 (C-4, C-9), 56.65 (C-5, C-10), 60.15 (C-1 ', C-1''), 68.45 (C-3, C-8), 71.58 (C-1, C-6), 82.67 (C-10b, C-10s).
Масс-спектр (MALDI TOF/TOF), m/z (Ioтн, %): 443 [М-Н]+ (100).Mass spectrum (MALDI TOF / TOF), m / z (I ont ,%): 443 [M-H] + (100).
Спектральные характеристики 2,7-дициклооктил-4,9-диметил-2,3а,5а,7,8а,10а-гексаазапергидропирена:Spectral characteristics of 2,7-dicyclooctyl-4,9-dimethyl-2,3a, 5a, 7,8a, 10a-hexaazaperhydropyrene:
Спектр ЯМР 1Н, δ, м.д. (J, Гц): 1.01 д (6Н, СН3, Н-11, 12, J=7.5), 1.40-1.60 м (20Н, СН2, Н а -2', 2'', 3', 3'', 7', 7'', 8', 8''; Н-4', 4'', 5', 5'', 6', 6''), 1.65-1.75 м (4Н, СН2, Hb-3', 3'', 7', 7''), 1.78-1.88 м (4Н, СН2, Hb-2', 2'', 8', 8''), 1.99 т (2Н, СН2, На-5, 10, 2Jab=13), 2.37 уш. с (2Н, СН, Н-10b, 10с), 2.40-2.50 м (2Н, СН2, Hb-5, 10; 2Н, СН, Н-4, 9), 2.81 д (2Н, СН2, Н а -3, 8, 2Jab=12), 2.88 д (2Н, СН2, Н а -1, 6, 2Jab=12), 2.95-3.05 м (2Н, СН, Н-1', 1''), 3.71 д (2Н, СН2, Hb-1, 6, 2Jba=12), 4.09 д (2Н, СН2, Hb-3, 8, 2Jba=12).NMR spectrum 1 H, δ, ppm (J, Hz): 1.01 d (6H, CH 3 , H-11, 12, J = 7.5), 1.40-1.60 m (20H, CH 2 , H a -2 ', 2 ", 3', 3 '',7', 7 '', 8 ', 8'';H-4', 4 '', 5 ', 5'',6', 6 ''), 1.65-1.75 m (4H, CH 2 , H b -3 ', 3 ", 7', 7"'), 1.78-1.88 m (4H, CH 2 , H b -2', 2 ", 8 ', 8"'), 1.99 t (2H , CH 2 , H a -5, 10, 2 J ab = 13), 2.37 br. with (2H, CH, H-10b, 10s), 2.40-2.50 m (2H, CH 2 , H b -5, 10; 2H, CH, H-4, 9), 2.81 d (2H, CH 2 , H a -3, 8, 2 J ab = 12), 2.88 d (2H, CH 2 , H a -1, 6, 2 J ab = 12), 2.95-3.05 m (2H, CH, H-1 ', 1 ""), 3.71 d (2H, CH 2 , H b -1, 6, 2 J ba = 12), 4.09 d (2H, CH 2 , H b -3, 8, 2 J ba = 12).
Спектр ЯМР 13С, δ, м.д.: 16.74 (С-11, С-12), 24.48 (С-3', С-3'', С-7', С-7''), 26.13 (С-5', С-5''), 27.25 и 27.31 (С-4', С-4'', С-6', С-6''), 29.06 и 29.38 (С-2', С- 2'', С-8', С-8'') 51.58 (С-4, С-9), 56.65 (С-5, С-10), 58.33 (С-1', С-1''), 68.40 (С-3, С-8), 71.61 (С-1, С-6), 82.71 (С-10b, С-10с).NMR spectrum 13 C, δ, ppm: 16.74 (C-11, C-12), 24.48 (C-3 ', C-3 ", C-7', C-7"), 26.13 ( C-5 ', C-5''), 27.25 and 27.31 (C-4', C-4 '', C-6 ', C-6''), 29.06 and 29.38 (C-2', C- 2 ", C-8", C-8 ") 51.58 (C-4, C-9), 56.65 (C-5, C-10), 58.33 (C-1 ', C-1") , 68.40 (C-3, C-8), 71.61 (C-1, C-6), 82.71 (C-10b, C-10s).
Масс-спектр (MALDI TOF/TOF), m/z (Ioтн, %):511 [М+К]+(100), 495 [M+Na]+ (50), 471 [М-Н]+ (10).Mass Spectrum MALDI TOF / TOF, m / z (I otn ,%): 511 [M + K] + (100), 495 [M + Na] + (50), 471 [M – H] + ( ten).
Спектральные характеристики 2,7-дибицикло[2.2.1]гепт-2-ил-4,9-диметил-2,3а,5а,7,8а,10а-гексаазапергидропирена:The spectral characteristics of 2,7-dibicyclo [2.2.1] hept-2-yl-4,9-dimethyl-2,3a, 5a, 7,8a, 10a-hexa-zaperhydropyrene:
Спектр ЯМР 1Н, δ, м.д. (J, Гц): 0.95-1.12 м (6Н, СН3, Н-11, 12; 6Н, СН2, Н а -3', 3'', 6', 6'', 7', 7''), 1.30-1.55 м (10Н, СН2, Hb-3', 3'', 6', 6'', 7', 7''; Н-5', 5''), 1.92-2.04 м (2Н, СН2, H a -5, 10), 2.24 уш. с (2Н, СН, Н-4', 4''), 2.30 уш. с (2Н, СН, Н-2', 2''), 2.60-2.78 м (2Н, СН2, Hb-5, 10; 4Н, СН, Н-4, 9, 10b, 10с), 2.70-2.82 м (2Н, СН, Н-1', 1''; 4Н, СН2, Н а -1, 3, 6, 8), 3.70-3.82 м (2Н, СН2, Hb-1, 6), 4.12-4.20 м (2Н, СН2, Hb-3, 8).NMR spectrum 1 H, δ, ppm (J, Hz): 0.95-1.12 m (6H, CH 3 , H-11, 12; 6H, CH 2 , H a- 3 ', 3 ", 6', 6", 7 ', 7 " ), 1.30-1.55 m (10H, CH 2 , H b -3 ', 3 ", 6', 6", 7 ', 7 ";H-5',5"'), 1.92-2.04 m (2H, CH 2 , H a -5, 10), 2.24 br. with (2H, CH, H-4 ', 4 ""), 2.30 br. with (2H, CH, H-2 ', 2 "), 2.60-2.78 m (2H, CH 2 , H b -5, 10; 4H, CH, H-4, 9, 10b, 10s), 2.70- 2.82 m (2H, CH, H-1 ', 1 "; 4H, CH 2 , H a -1, 3, 6, 8), 3.70-3.82 m (2H, CH 2 , H b -1, 6) 4.12-4.20 m (2H, CH 2 , H b -3, 8).
Спектр ЯМР 13С, δ, м.д.: 16.80 (С-11, С-12), 27.66 (С-6', С-6''), 28.40 (С-7', С-7''), 35.21 (С-3', С-3''), 36.31 (С-4', С-4'') 37.45 (С-5', С-5''), 38.40 (С-2', С-2''), 51.53 (С-4', С-9), 56.58 (С-5, С-10), 62.57 (С-1', С-1'') 68.82 (С-3, С-8), 72.64 (С-1, С-6), 82.56 (С-10b, С-10с).Nuclear Magnetic Resonance Spectrum 13 C, δ, ppm: 16.80 (C-11, C-12), 27.66 (C-6 ', C-6''), 28.40 (C-7', C-7 '') , 35.21 (C-3 ', C-3 "), 36.31 (C-4', C-4 '') 37.45 (C-5 ', C-5"'), 38.40 (C-2 ', C -2 ""), 51.53 (C-4 ', C-9), 56.58 (C-5, C-10), 62.57 (C-1', C-1 ") 68.82 (C-3, C- 8), 72.64 (C-1, C-6), 82.56 (C-10b, C-10s).
Масс-спектр (MALDI TOF/TOF), m/z (Ioтн, %): 439 [М-Н]+ (100).Mass spectrum (MALDI TOF / TOF), m / z (I ont ,%): 439 [M-H] + (100).
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| US4904779A (en) * | 1988-01-23 | 1990-02-27 | Basf Aktiengesellschaft | Heterocycles based on piperazinopiperazine |
| RU2561506C1 (en) * | 2014-04-04 | 2015-08-27 | Федеральное государственное бюджетное учреждение науки Институт нефтехимии и катализа Российской академии наук | METHOD OF OBTAINING 2,7-DIALKYL-2,3a,5a,7,8a,10a-HEXAAZAPERHYDROPYRENES |
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| US4904779A (en) * | 1988-01-23 | 1990-02-27 | Basf Aktiengesellschaft | Heterocycles based on piperazinopiperazine |
| RU2561506C1 (en) * | 2014-04-04 | 2015-08-27 | Федеральное государственное бюджетное учреждение науки Институт нефтехимии и катализа Российской академии наук | METHOD OF OBTAINING 2,7-DIALKYL-2,3a,5a,7,8a,10a-HEXAAZAPERHYDROPYRENES |
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| E. B. Rakhimova et al. "An efficient catalytic method for the synthesis of 2,7-dialkyl-2,3a,5a,7,8a,10a-hexaazaperhydropyrenes" Tetrahedron letters, 2014, vol.55, 6367-6369. * |
| E. Rakhimova et al. "New Catalytic Method for the Synthesis of 2,7-Dicycloalkyl-hexaazaperhydropyrenes" Journal of Chemistry, 2016, 1-6. * |
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