Synthesis, crystal structure, and interconversions of new N-aryl-1,3,5-dithiazinanes, 1,3,5-thiadiazinanes, and 1,5-dithia-3,7-diazacyclooctanes

Ахметова, В. Р.; Niatshina, Z. T.; Khabibullina, G. R.; Бушмаринов, Иван С.; Borisova, A. O.; Starikova, Z. A.; Korzhova, L. F.; Кунакова, Р. В.

doi:10.1007/s11172-010-0196-y

Cited by 10 publications

(4 citation statements)

References 16 publications

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“…Two compounds with alternate S and N heteroatoms have been reported. One is 1,5-dithia-3,7-diazacyclooctane with a crown conformation, 7 and the one is trans-5,10-bis-(methoxycarbonyl)-5,10-diphenyldipyrazolo[l,5-a:l′,5′-e]- [1,5]diaza [3,6]dithiocine. 8 Heterocyclic compounds with four nitrogen atoms have also been less reported; one is the energetic material 1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane.…”

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Synthesis and Characterization of an Eight-Membered Heterocyclic 1,3,5,7-Tetra(3-pyridyl)-1,3,5,7-tetrazacyclooctane

Li,

Dai,

Zhu

et al. 2023

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N,N′-Bis(3-pyridyl)methanediamine was prepared by treating 3-aminopyridine with formaldehyde in acetonitrile. By treating it with formaldehyde, the eight-membered heterocyclic ring compound 1,3,5,7-tetra(3-pyridyl)-1,3,5,7-tetrazacyclooctane was prepared. This could occur in a two-step manner in a [3+1+3+1] cycloaddition reaction. The compounds were characterized by X-ray crystallography, 1H and 13C NMR spectroscopy, and mass spectrometry. The powder XRD pattern of 1,3,5,7-tetra(3-pyridyl)-1,3,5,7-tetrazacyclooctane was also determined and revealed an uncommon twist-crown conformation, which was further confirmed by DFT calculations.

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Synthesis and Characterization of an Eight-Membered Heterocyclic 1,3,5,7-Tetra(3-pyridyl)-1,3,5,7-tetrazacyclooctane

Li,

Dai,

Zhu

et al. 2023

SynOpen

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“…One-pot methods of synthesis of heterocycles possessing practically useful properties based on the cyclothiomethylation of primary amines with formaldehyde and H 2 S [1][2][3] are interesting for the development of modern ecologically friendly chemical technology. Many sulfur and nitrogen heterocycles possess a biocidal activity [4], and also fi nd application as selective complexing agents [5], extractants, and sorbents for noble metals [6].…”

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Cyclothiomethylation of heterochain α,ω-diamines with formaldehyde and H2S

et al. 2012

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Cyclothiomethylation was performed of heterochain (O, S-S, NH) α,ω-diamines with formaldehyde and H 2 S in aqueous medium at 20-60°С to obtain new α,ω-bis(1,3,5-dithiazinanes). The cyclocondensation of N-(3-aminopropyl)butane-1,4-diamine (spermidine), formaldehyde, and H 2 S proceeds effi ciently in the medium of BuOH-H 2 O at 0°С and leads to the formation of previously unknown O,S-containing macroheterocycle, 1,7-dioxa-3,5,9,11-tetrathiacyclododecane. A fungicidal activity was found in 5,5'-(3,6-dioxaoctane-1,8-diyl)bis-1,3,5-dithiazinane with respect to microscopic fungi affecting agriculture.One-pot methods of synthesis of heterocycles possessing practically useful properties based on the cyclothiomethylation of primary amines with formaldehyde and H 2 S [1-3] are interesting for the development of modern ecologically friendly chemical technology. Many sulfur and nitrogen heterocycles possess a biocidal activity [4], and also fi nd application as selective complexing agents [5], extractants, and sorbents for noble metals [6].It was shown previously [7] that the condensation of α,ω-diamines I with CH 2 O and H 2 S (Scheme 1) at 60°С occurred with the formation of α,ω-bis(1,3,5-dithiazinan-5-yl)-alkanes II, and at 0°С the direction of the reaction changed, and the main reaction products were 3-thia-1,5-diazabicyclo[n.3.1] alkanes III.In extension of the study of the α,ω-diamines cyclothiomethylation and also aiming at testing the possibility to perform the cyclothiomethylation of aliphatic heterochain α,ω-diamines containing C-O, S-S, and С-N bonds and to obtain new classes of heterocycles we investigated the reactions of α,ω-diamines with CH 2 O and H 2 S. The cyclothiomethylation of 3-oxapentane-1,5-diamine (IV) and 3,6-dioxaoctane-1,8-diamine (V) with formaldehyde and H 2 S in the mentioned conditions (molar ratio 1 : 3 : 2 or 1 : 6 : 4, H 2 O, 0-60°С, 3 h) proceeded at the terminal NH 2 groups of the initial diamine giving 5,5'-(3-oxapentane-1,5-diyl)bis-1,3,5-dithiazinane (VI) and 5,5'-(3,6-dioxaoctane-1,8-diyl) bis-1,3,5-dithiazinane (VII) (Scheme 2). All our attempts to direct the cyclothiomethylation of diamines IV and V to the route of the intramolecular condensation by reducing the reaction temperature to -30°С failed (Table 1).Dithiazinanes VI and VII were isolated from the reaction mixture by extraction with chloroform followed by Scheme 1. N N S n H 2 N NH 2 N N S S S S n n 60 o C 0 o C II III I CH 2 O _ H 2 S CH 2 O _ H 2 S n = 1 _ 8.

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“…1,3,5-Dithiazinanes can also be obtained by transamination with N-tert-butyl-1,3,5-dithiazinane [9] or by reaction of hydrogen sulfide with 1,3,5-trimethyl-1,3,5-triazinane formed by condensation of methylamine with formaldehyde [10]. There are no published data on the synthesis of 1,3,5-dithiazinanes and 1,3,5-thiadiazinanes by thiomethylation of heteroaromatic amines, many of which possess various kinds of biological activity (fungicidal, antimicrobial, antitumor, and antioxidant) [11,12].…”

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“…We previously showed that substituted anilines undergo thiomethylation with CH 2 O-H 2 S and that the reaction direction depends on both the conditions and structural specificity of the substrate DOI: 10 With a view to obtain thermodynamically less stable 1,3,5-thiadiazinanes the reaction was carried out at 0°C at a substrate-CH 2 O-H 2 S ratio of 2 : 3 : 2 [9]. Thiomethylation of hetarylamines Ia-Il was performed under analogous conditions, but only 5-methylisoxazol-3-amine (Ia) behaved similarly to anilines.…”

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Thiomethylation of heteroaromatic amines

et al. 2011

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Thiomethylation of heteroaromatic amines with formaldehyde-hydrogen sulfide gave linear and cyclic heteroatom compounds: N,N′-[methylenebis(sulfanediylmethylene)]bishetarenamines and 5 3,]bishetarenamines were found to undergo transformation into 5-hetaryl-1,3,5-dithiazinanes by the action of CH 2 O-H 2 S. Transamination of 5-methyl-1H-pyrazol-3-amine, 6-nitro-1,3-benzothiazol-2-amine, and 5-bromopyridin-2-amine with 5-methyl-1,3,5-dithiazinane selectively afforded the corresponding 5-hetaryl-1,3,5-dithiazinanes.One-pot thiomethylation of amines with the CH 2 O-H 2 S system [1] provides a simple and efficient synthetic route to 1,3,5-thiadiazinanes and 1,3,5-dithiazinanes [2-5], some of which were found to exhibit bactericidal, herbicidal, fungicidal, insecticidal, acaricidal, and antimicrobial activity [6-8].1,3,5-Dithiazinanes can also be obtained by transamination with N-tert-butyl-1,3,5-dithiazinane [9] or by reaction of hydrogen sulfide with 1,3,5-trimethyl-1,3,5-triazinane formed by condensation of methylamine with formaldehyde [10]. There are no published data on the synthesis of 1,3,5-dithiazinanes and 1,3,5-thiadiazinanes by thiomethylation of heteroaromatic amines, many of which possess various kinds of biological activity (fungicidal, antimicrobial, antitumor, and antioxidant) [11,12].In the present work we examined both synthetic approaches to 1,3,5-thiadiazinanes and 1,3,5-dithiazinanes via thiomethylation of 5-methylisoxazol-3-amine (Ia), 5-methyl-1H-pyrazol-3-amine (Ib), 4-methyl-, 5-methyl-, 4-phenyl-and 5-nitrothiazol-2-amines IcIf, 6-nitro-1,3-benzothiazol-2-amine (Ig), pyridine-2-amine (Ih), pyridine-3-amine (Ii), pyridine-4-amine (Ij), 4-methylpyridin-2-amine (Ik), and 5-bromopyridin-2-amine (Il). We previously showed that substituted anilines undergo thiomethylation with CH 2 O-H 2 S and that the reaction direction depends on both the conditions and structural specificity of the substrate

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Synthesis, crystal structure, and interconversions of new N-aryl-1,3,5-dithiazinanes, 1,3,5-thiadiazinanes, and 1,5-dithia-3,7-diazacyclooctanes

Cited by 10 publications

References 16 publications

Synthesis and Characterization of an Eight-Membered Heterocyclic 1,3,5,7-Tetra(3-pyridyl)-1,3,5,7-tetrazacyclooctane

Synthesis and Characterization of an Eight-Membered Heterocyclic 1,3,5,7-Tetra(3-pyridyl)-1,3,5,7-tetrazacyclooctane

Cyclothiomethylation of heterochain α,ω-diamines with formaldehyde and H2S

Thiomethylation of heteroaromatic amines

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