5-Methyl-1,3,5-dithiazinane

• CAS: 6302-94-9
• Catalog Number: ACM6302949
• Category: Main Products
• Molecular Weight: 135.25
• Molecular Formula: C4H9NS2
• Synonyms: Dihydro-5-methyl-4H-1,3,5-dithiazine
• Melting Point: 63-65°C
• Appearance: White to Off-White Solid

Case Study

Application of 5-Methyl-1,3,5-dithiazinane in Heteroaromatic Amine Thiomethylation

Akhmetova, V. R., et al. Russian Journal of Organic Chemistry 47.6 (2011): 920-927.

5-methyl-1,3,5-dithiazinane (abbreviated here as dithiazinane V) enables formation of cyclic 1,3,5-dithiazinanes bearing heteroaromatic substituents via thermal or, more effectively, catalytic transamination with heteroaromatic amines. Under mild catalytic conditions (SmCl3·6H2O, 5 mol %, CHCl3, 20 °C, 3 h) several heteroaryl amines were converted to their corresponding N-hetaryl-1,3,5-dithiazinanes in ≈70% isolated yields, demonstrating the reagent's practicality for preparing these sulfur-containing heterocycles.
Thermal Transamination: equimolar amounts of hetarylamine and dithiazinane heated in refluxing chloroform (≈60 °C) for extended times (24 h). Conversions varied widely (10-80%) and isolated yields of target dithiazinanes under thermal conditions were often low (10-20%) for many substrates.
Catalytic Transamination: dithiazinane (0.7 mmol) and hetarylamine (0.35 mmol; 2:1 dithiazinane:amine molar ratio) stirred in chloroform at 20 °C for 3 h in the presence of 5 mol % SmCl3·6H2O under argon. After a simple workup (passage through silica gel and evaporation) the desired N-hetaryl-1,3,5-dithiazinanes were obtained in substantially higher yields. Other salts screened included NiCl2·6H2O, FeCl3·6H2O and Sm(NO3)3·6H2O; samarium(III) chloride hexahydrate performed best in the series.

5-Methyl-1,3,5-dithiazinane as a Versatile Building Block in Heterocyclic Synthesis

Rakhimova, E. B., I. V. Ozden, et al. Russian Journal of Organic Chemistry 54.7 (2018): 961-986.

5-Methyl-1,3,5-dithiazinane is a cyclic N-methylated dithiazinane that acts as a stable, isolable thiomethylating/transamination donor. It behaves as a masked "S-CH2-" transfer reagent and as a transamination partner: when combined with primary aromatic amines under suitable catalysis it delivers N-substituted 1,3,5-dithiazinanes.
Synthetic Routes & Conditions
1. Catalytic transamination with N-methyl-1,3,5-dithiazinane
General catalytic protocol: 5-methyl-1,3,5-dithiazinane (excess) with the heteroaromatic primary amine in chloroform at 20 °C in the presence of 5 mol% Sm(NO3)3·6H2O (samarium catalyst) or other Lewis/lanthanide salts. Reaction times reported ≈ 3 h. Under these mild catalytic conditions several aromatic and heteroaromatic amines gave N-aryl / N-hetaryl 1,3,5-dithiazinanes in 51-91% yields; for aniline an example of 68% yield was reported under a samarium catalyst.
2. Recyclization of 1,3,5-trithiane with primary amines
1,3,5-trithiane reacted with aromatic primary amines in the presence of 5 mol% FeCl3·6H2O (iron salt catalyst) to give the corresponding 1,3,5-dithiazinanes selectively in 60-86% yields. This route is an alternative to dithiazinane transamination and is effective for a range of arylamines.
3. Extensions - diamines and hydrazines
Diamines: Catalytic transamination with aromatic diamines and 5 mol% Sm(NO3)3·6H2O furnished bis-1,3,5-dithiazinanes in ~50-58% yields.
Arylhydrazines: Mild catalytic transamination using CoCl2/γ-Al2O3 at 20 °C produced N-aryl(benzyl)-1,3,5-dithiazinan-5-amines and nitro-substituted analogues in >80% yields; in the absence of catalyst yields were ≤15%. Alternatively, Cp2TiCl2 catalyzed recyclization of 1,3,5-trithiane with arylhydrazines to afford similar products in 60-69% yields.

Custom Q&A

What is the molecular formula of 5-Methyl-1,3,5-dithiazinane?

The molecular formula of 5-Methyl-1,3,5-dithiazinane is C4H9NS2.

What are the synonyms of 5-Methyl-1,3,5-dithiazinane?

The synonyms of 5-Methyl-1,3,5-dithiazinane include dihydro-5-methyl-4H-1,3,5-dithiazine, NSC41551, T8MXD3T7ZZ, and more.

What is the CAS number of 5-Methyl-1,3,5-dithiazinane?

The CAS number of 5-Methyl-1,3,5-dithiazinane is 6302-94-9.

What is the InChI of 5-Methyl-1,3,5-dithiazinane?

The InChI of 5-Methyl-1,3,5-dithiazinane is InChI=1S/C4H9NS2/c1-5-2-6-4-7-3-5/h2-4H2,1H3.

What is the molecular weight of 5-Methyl-1,3,5-dithiazinane?

The molecular weight of 5-Methyl-1,3,5-dithiazinane is 135.3 g/mol.

How many hydrogen bond acceptor counts does 5-Methyl-1,3,5-dithiazinane have?

5-Methyl-1,3,5-dithiazinane has 3 hydrogen bond acceptor counts.

What is the topological polar surface area of 5-Methyl-1,3,5-dithiazinane?

The topological polar surface area of 5-Methyl-1,3,5-dithiazinane is 53.8 Ų.

How many heavy atom counts are there in 5-Methyl-1,3,5-dithiazinane?

5-Methyl-1,3,5-dithiazinane has 7 heavy atom counts.

Is 5-Methyl-1,3,5-dithiazinane a covalently-bonded unit?

Yes, 5-Methyl-1,3,5-dithiazinane is a covalently-bonded unit.

Is 5-Methyl-1,3,5-dithiazinane a canonicalized compound?

Yes, 5-Methyl-1,3,5-dithiazinane is a canonicalized compound.