{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,14]],"date-time":"2026-07-14T15:19:46Z","timestamp":1784042386419,"version":"3.55.0"},"reference-count":32,"publisher":"MDPI AG","issue":"17","license":[{"start":{"date-parts":[[2023,8,22]],"date-time":"2023-08-22T00:00:00Z","timestamp":1692662400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100006769","name":"Russian Science Foundation","doi-asserted-by":"publisher","award":["23-23-00656"],"award-info":[{"award-number":["23-23-00656"]}],"id":[{"id":"10.13039\/501100006769","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["IJMS"],"abstract":"<jats:p>1,1-Dimethylhydrazine (Heptil, rocket fuel (UDMH)) is characterized by extremely high toxicity, teratogenicity and the ability to constantly absorb water from the atmosphere, losing its energy characteristics. In this regard, as well as due to the alternative fuel (\u201cAngara\u201d) transition, there is a need for UDMH utilization in huge amounts. A more benign approach involves its immediate reaction with a formalin solution to form 1,1\u2013dimethyl-2-methylene hydrazone (MDH), which is significantly less toxic by an order of magnitude. MDH can then be polymerized under acidic conditions, and the resulting product can be burned, yielding a substantial amount of nitrogen oxides. We propose an alternative to incineration by involving MDH in organic synthesis. We studied the reactions of MDH and its analog N,N-dimethyl-2-(methylenamino)ethane-1-amine (MDEA) with available CH-acids: tetracyanoethylated ketones (TCEKs) based on cyclohexanone, 4-propylcyclohexanone, 2-methylcyclohexanone, cyclododecanone and tetracyanoethane. The structures synthesized were confirmed by IR, 1H, 13C NMR and mass spectroscopy methods. MDH-based adducts were also identified by X-ray structural analysis. TCEKs and MDH, as well as TCEK based on cyclohexanone and MDEA, form bi- and tricyclic structures: pyrrolo [3,4c]-quinolines (using TCEKs based on cyclohexanone and 4-propylcyclohexanone), epiminomethanoquinoline-3,4-dicarbonitrile (using TCEK based on 2-methylcyclohexanone) and cyclododec[b]pyran-3,4-dicarbonitrile (using TCEK based on cyclododecanone). MDH and TCNEH2 formed a pyrrole derivative. Thus, we synthesized the structures that are of interest for molecular design and pharmaceutical chemistry.<\/jats:p>","DOI":"10.3390\/ijms241713076","type":"journal-article","created":{"date-parts":[[2023,8,23]],"date-time":"2023-08-23T07:25:24Z","timestamp":1692775524000},"page":"13076","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Treatment of Substandard Rocket Fuel 1,1-Dimethylhydrazine via Its Methylene Derivative into Heterocycles Based on Pyrrolo-[3,4c]Quinolines, Cyclododeca[b]piran and Pyrrole"],"prefix":"10.3390","volume":"24","author":[{"given":"Elizaveta","family":"Ivanova","sequence":"first","affiliation":[{"name":"Organic and Pharmaceutical Chemistry Department, ssUlyanov Chuvash State University, Moskovsky Prospect, 15, 428015 Cheboksary, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Maxim","family":"Maryasov","sequence":"additional","affiliation":[{"name":"Organic and Pharmaceutical Chemistry Department, ssUlyanov Chuvash State University, Moskovsky Prospect, 15, 428015 Cheboksary, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Vera","family":"Andreeva","sequence":"additional","affiliation":[{"name":"Organic and Pharmaceutical Chemistry Department, ssUlyanov Chuvash State University, Moskovsky Prospect, 15, 428015 Cheboksary, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Margarita","family":"Osipova","sequence":"additional","affiliation":[{"name":"Organic and Pharmaceutical Chemistry Department, ssUlyanov Chuvash State University, Moskovsky Prospect, 15, 428015 Cheboksary, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tatyana","family":"Vasilieva","sequence":"additional","affiliation":[{"name":"Organic and Pharmaceutical Chemistry Department, ssUlyanov Chuvash State University, Moskovsky Prospect, 15, 428015 Cheboksary, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Alexey","family":"Eremkin","sequence":"additional","affiliation":[{"name":"Organic and Pharmaceutical Chemistry Department, ssUlyanov Chuvash State University, Moskovsky Prospect, 15, 428015 Cheboksary, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9614-5092","authenticated-orcid":false,"given":"Olga","family":"Lodochnikova","sequence":"additional","affiliation":[{"name":"Organic and Pharmaceutical Chemistry Department, Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Streed, 8, 420088 Kazan, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Denis","family":"Grishaev","sequence":"additional","affiliation":[{"name":"Organic and Pharmaceutical Chemistry Department, Scientific and Educational Center Pharmacy, Kazan Federal University, Paris Commune Street, 9, 296100 Kazan, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Oleg E.","family":"Nasakin","sequence":"additional","affiliation":[{"name":"Organic and Pharmaceutical Chemistry Department, ssUlyanov Chuvash State University, Moskovsky Prospect, 15, 428015 Cheboksary, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2023,8,22]]},"reference":[{"key":"ref_1","unstructured":"Kolesnikov, S.V. (2014). General Information about Fuel\u20141,1 Dimethylhydrazine, Oxidation of Asymmetric Dimethylhydrazine (Heptyl) and Identification of Its Transformation Products in Straits: Monograph, SibAK Publishing House."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1002\/jlac.19415470102","article-title":"Untersuchungen in der Hydrazinreihe. I. Die Darstellung von Tri- und Tetra-alkyl-hydrazinen","volume":"547","author":"Klages","year":"1941","journal-title":"Justus Liebig\u2019s Ann. Chem."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"2783","DOI":"10.1021\/ja01544a053","article-title":"Cyanocarbon Chemistry. III.1Addition Reactions of Tetracyanoethylene","volume":"80","author":"Middleton","year":"1958","journal-title":"J. Am. Chem. Soc."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"4031","DOI":"10.1016\/j.bmcl.2006.05.008","article-title":"Effect of substitution on novel tricyclic HIV-1 integrase inhibitors","volume":"16","author":"Fardis","year":"2006","journal-title":"Bioorganic Med. Chem. Lett."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"1893","DOI":"10.1016\/0960-894X(96)00343-5","article-title":"Synthesis and activity of staurosporine analogs with a lactone functionality","volume":"6","author":"Yamada","year":"1996","journal-title":"Bioorganic Med. Chem. Lett."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"7040","DOI":"10.1021\/jo00126a071","article-title":"Oteromycin: A Novel Antagonist of Endothelin Receptor","volume":"60","author":"Singh","year":"1995","journal-title":"J. Org. Chem."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"3906","DOI":"10.1016\/j.bmcl.2006.05.034","article-title":"Diaryl substituted pyrrolidinones and pyrrolones as 5-HT2C inhibitors: Synthesis and biological evaluation","volume":"16","author":"Micheli","year":"2006","journal-title":"Bioorganic Med. Chem. Lett."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"4715","DOI":"10.1016\/j.bmcl.2006.07.011","article-title":"4-Amino-2-alkyl-butyramides as small molecule CCR2 antagonists with favorable pharmacokinetic properties","volume":"16","author":"Butora","year":"2006","journal-title":"Bioorganic Med. Chem. Lett."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"403","DOI":"10.1016\/0223-5234(91)90101-R","article-title":"Amnesia-reversal activity of a series of 5-alkoxy-1-arylsulfonyl-2-pyrrolidinones","volume":"26","author":"Toja","year":"1991","journal-title":"Eur. J. Med. Chem."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"1771","DOI":"10.1021\/acs.molpharmaceut.7b00028","article-title":"N,N-Dimethyl Tertiary Amino Group Mediated Dual Pancreas- and Lung-Targeting Therapy against Acute Pancreatitis","volume":"14","author":"Luo","year":"2017","journal-title":"Mol. Pharm."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"3760","DOI":"10.1016\/j.bmc.2013.04.034","article-title":"Synthesis and pharmacological investigation of new N-hydroxyalkyl-2-aminophenothiazines exhibiting marked MDR inhibitory effect","volume":"21","author":"Egyed","year":"2013","journal-title":"Bioorganic Med. Chem."},{"key":"ref_12","first-page":"2654","article-title":"Steady-State Pharmacokinetic Properties of a 24-Hour Prolonged-Release Formulation of Ropinerole: Results of Two Randomized Studies in Patients with Parkinson\u2019s Disease","volume":"29","author":"Tompson","year":"2007","journal-title":"Clin. Pharmacokinet."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"102872","DOI":"10.1016\/j.jevs.2019.102872","article-title":"Persistent bilateral mydriasis associated with pituitary adenoma in horses","volume":"85","author":"Allnoch","year":"2020","journal-title":"J. Equine Vet. Med."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"105562","DOI":"10.1016\/j.tvjl.2020.105562","article-title":"Efficacy of pergolide for the treatment of intermediate pituitary dysfunction in horses: A systematic review","volume":"266","author":"Tatum","year":"2020","journal-title":"Vet. J."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"791","DOI":"10.1124\/jpet.102.039867","article-title":"Differential actions of antiparkinson agents at multiple classes of monoaminergic receptor. I. A multivariate analysis of the binding profiles of 14 drugs at 21 native and cloned human receptor subtypes","volume":"303","author":"Millan","year":"2002","journal-title":"J Pharm. Exp. Ther."},{"key":"ref_16","doi-asserted-by":"crossref","unstructured":"Assion, H.J. (2004). Malignes Neuroleptisches Syndrom, Georg Thieme Verlag.","DOI":"10.1055\/b-002-19473"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"959","DOI":"10.1111\/j.1460-9568.1996.tb01583.x","article-title":"Activation of meningeal 5-HT2B receptors: An early step in the generation of migraine headache?","volume":"8","author":"Schmuck","year":"1996","journal-title":"Eur. J. Neurosci."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"681","DOI":"10.1007\/s00115-004-1830-4","article-title":"Apomorphin bei der Behandlung des Morbus Parkinson","volume":"76","author":"Dressler","year":"2005","journal-title":"Der Nervenarzt"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"449","DOI":"10.1002\/med.10067","article-title":"Selective human enterovirus and rhinovirus inhibitors: An overview of capsid-binding and protease-inhibiting molecules","volume":"24","author":"Shih","year":"2004","journal-title":"Med. Res. Rev."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"4367","DOI":"10.1021\/ja01501a063","article-title":"Cyanocarbon Chemistry. XV.1A New Synthesis of 3,4-Dicyano-2(1H)-pyridones","volume":"82","author":"Dickinson","year":"1960","journal-title":"J. Am. Chem. Soc."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"2143","DOI":"10.1016\/j.tetlet.2013.02.043","article-title":"Domino synthesis of 3-amino-8-hydroxy-1,6-dioxo-2,7-diazaspiro[4.4]non-3-ene-4-carbonitriles","volume":"54","author":"Fedoseev","year":"2013","journal-title":"Tetrahedron Lett."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"6407","DOI":"10.1016\/j.tetlet.2011.09.084","article-title":"Reaction between 4-oxoalkane-1,1,2,2-tetracarbonitriles and morpholine: Regioselective synthesis of 5-amino-2-(morpholin-4-yl)-3-(2-oxoalkyl)-3H-pyrrol-3,4-dicarbonitriles","volume":"52","author":"Belikov","year":"2011","journal-title":"Tetrahedron Lett."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"1374","DOI":"10.1134\/S1070428006090211","article-title":"Isopropylidenemalononitrile in the synthesis of 2-amino-4,6,6-trimethylcyclohexa-2,4-diene-1,1,3-tricarbonitrile, 6-amino-2-(4-methoxybenzoylmethylsulfanyl)-4,4-dimethyl-1,4-dihydropyridine-3,5-dicarbonitrile, and fused 2-aminopyrans according to Michael","volume":"42","author":"Dyachenko","year":"2006","journal-title":"Russ. J. Org. Chem."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"1335","DOI":"10.1055\/s-1997-1035","article-title":"In the Dark and in the Light: Homogeneous and Heterogeneous Catalytic Activation of 1,2-Diazenes","volume":"12","author":"Kisch","year":"2000","journal-title":"Synlett"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"3615","DOI":"10.1021\/jo00836a006","article-title":"Heterocyclic studies. 33. 5-Methyl-6-phenyl-1,2-diazabicyclo[3.2.0]-2,6-heptadiene-4-one. Thermolysis to 4-methyl-5-phenylpyridazine","volume":"35","author":"Voelker","year":"1970","journal-title":"J. Org. Chem."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"1342","DOI":"10.1021\/jo01280a014","article-title":"Heterocyclic studies. XXIII. The cleavage of 2,3-dihydro-1,2-diazepin-4-ones with base","volume":"32","author":"Moore","year":"1967","journal-title":"J. Org. Chem."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"4033","DOI":"10.1021\/acs.joc.9b00034","article-title":"Too Short-Lived or Not Existing Species: N-Azidoamines Reinvestigated","volume":"84","author":"Banert","year":"2019","journal-title":"J. Org. Chem."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"1815","DOI":"10.1021\/jo00900a029","article-title":"Structure determination of the N-methyl isomers of 5-amino-3,4-dicyanopyrazole and certain related pyrazolo[3,4-d]pyrimidines","volume":"40","author":"Hecht","year":"1975","journal-title":"J. Org. Chem."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"1613","DOI":"10.1134\/S1070363221090024","article-title":"Synthesis of 2,2-Dimethylhydrazonebut-2-enenitriles and [(2,2-Dimethylhydrazono)methyl]phenylacrylonitriles for Development of Antimicrobial Fluorescent Dyes","volume":"91","author":"Maryasov","year":"2021","journal-title":"Gen. Chem. J."},{"key":"ref_30","first-page":"3","article-title":"SHELXT: Integration of space group definition and structural solution","volume":"71","author":"Sheldrick","year":"2015","journal-title":"Act Crystallogr."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"112","DOI":"10.1107\/S0108767307043930","article-title":"A Brief History of SHELX","volume":"64","author":"Sheldrick","year":"2007","journal-title":"Act Crystallogr."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"453","DOI":"10.1107\/S002188980600731X","article-title":"Mercury: Visualization and analysis of crystal structures","volume":"39","author":"Macrae","year":"2006","journal-title":"J. Appl. Crystallogr."}],"container-title":["International Journal of Molecular Sciences"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1422-0067\/24\/17\/13076\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T20:39:57Z","timestamp":1760128797000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1422-0067\/24\/17\/13076"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,8,22]]},"references-count":32,"journal-issue":{"issue":"17","published-online":{"date-parts":[[2023,9]]}},"alternative-id":["ijms241713076"],"URL":"https:\/\/doi.org\/10.3390\/ijms241713076","relation":{},"ISSN":["1422-0067"],"issn-type":[{"value":"1422-0067","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,8,22]]}}}