Dimethyl N-cyanodithioiminocarbonate Research Articles

Co-crystallization of dimethyl N-cyanodithioiminocarbonate and bis[(aqua)-µ 2-hydroxy-n-butyldichlorotin(IV)

Abstract The one-pot reaction of dimethyl N-cyanodithioiminocarbonate, [(MeS)2C=N–C≡N] with n-butyltin trichloride, Sn(n-Bu)Cl3 led to a dinuclear complex [Sn(n-Bu)Cl2(OH)(H2O)]2 which co-crystallized with two [(MeS)2C=N–C≡N] molecules (1). The product was investigated by single-crystal X-ray diffraction analysis. Compound 1 crystallizes in the triclinic space group P 1 ‾ $P\bar{1}$ with a = 6.8048(6), b = 11.0645(9), c = 12.4240(10) Å, α = 66.3120(10), β = 75.6070(10), γ = 72.2940(10)°, V = 807.42(12) Å3, Z = 1 and Z′ = 0.5. In the complex, two aqua-n-butyltin dichloride, [Sn(n-Bu)Cl2(H2O)]+, moieties are bridged by two hydroxide OH− ions. Two inner O2–H2OB⋯Cl2 hydrogen bonds strengthen the dinuclear component which is connected to its neighbours through a O1–H1O⋯Cl1 hydrogen bond pattern giving rise to a network of infinite chains running parallel to the (100) direction. The dimethyl N-cyanodithioiminocarbonate molecules are linked to these infinite chains through O2–H2OA⋯N1 hydrogen bonding interactions of D type. The [(MeS)2C=N–CN] molecules exhibits a minor positional disorder. These hydrogen bonding interactions lead to cyclic patterns generating R 1 1 ( 6 ) ${\text{R}}_{1}^{1}\left(6\right)$ and R 2 2 ( 8 ) ${\text{R}}_{2}^{2}\left(8\right)$ rings. Weak C–H⋯Cl hydrogen bonds also contribute to the stability of the crystal structure.

DIMETHYL N-CYANODITHIOIMINOCARBONATE AND TRIPHENYLPHOSPHINE OXIDE METAL HALIDE COMPLEXES: MOLECULAR CRYSTAL ELUCIDATION

Two MX2 (M = Ni, Zn; X = Cl, Br) dimethyl N-cyanodithioiminocarbonate compounds and one CrCl2 triphenylphosphine oxide complex were isolated and elucidated by single crystal X-ray crystallography. NiCl2[(CH3S)2C═NC≡N]2 (1) features inversion-related hydrogen bonded dimers linked into chains interacting through C-H···Cl growing layers along [110] whose junction into a 3D structure is enabled by H-bonds. ZnBr2[(CH3S)2C═NC≡N]2 (2) also exhibits inversion-related H-bonded dimers. In contrast with 1, the structure of 2 comprises chains along [110], connected via C-H···Br and C-H···S into a 2D layer along [-110]. CrCl2(OPPh3)2 (3) obtaining undergone redox processes, oxidizing [CH3C(O)CH2PPh3]+ to form PPh3PO, and reducing Cr from CrVI to CrII. In the structure, each molecule is linked to height neighbors through H-bonds affording a 3D network.

Syntheses and Crystal Structures of Methyl N-Substituted-N′-Cyanocarbamimidothioates Derived from Dimethyl N-Cyanodithioiminocarbonate

Reaction of dimethyl N-cyanodithioiminocarbonate and arylamine or alkylamine compounds in the refluxing ethanol solution afforded the according methyl N-substituted-N′-cyanocarbamimidothioates 1–16 in good yields. Compounds 1–16 were characterized by proton nuclear magnetic resonance (1H NMR) and infrared spectroscopies, of which the structures of compounds 1, 2 and 3 (Elgemeie et al. in Acta Cryst E71:104–111, 2015) were established by X-ray crystallography, showing that weak hydrogen-bonding interactions exist in compounds 1–3. Compound 1 crystallizes in the orthorhombic space group Pbca, with a = 6.997(2), b = 7.395(2), c = 36.112(11) A, and Z = 8. The unit cell of 2 has a monoclinic P21/c symmetry with the cell parameters a = 5.8717(12), b = 4.6598(9), c = 37.799(9) A, β = 91.126(6)°, and Z = 4. Compound 3 crystallizes in the orthorhombic space group Pbca, with a = 7.123(3), b = 7.374(3), c = 38.538(16) A, and Z = 8. A series of methyl N-subsituted-N′-cyanocarbamimidothioate compounds were efficiently synthesized via the reaction of arylamine or alkylamine compounds with dimethyl N-cyanodithioiminocarbonate. The structures of compounds 1–3 were characterized by X-Ray crystallography.

Pyrimidine non-nucleoside analogs: A direct synthesis of a novel class of N-substituted amino and N-sulfonamide derivatives of pyrimidines

ABSTRACTA convenient method for the regioselective synthesis of pyrimidine non-nucleoside analogs was developed. This study reports a novel and efficient method for the synthesis of a new type of N-substituted amino methylsulfanylpyrimidines and the corresponding pyrazolo[3,4-d]pyrimidines. This series of compounds was designed through the reaction of dimethyl N-cyanodithioiminocarbonate with 2-cyano-N′-(thiophen-2-yl-, furan-2-yl- and pyridin-4-ylmethylene)acetohydrazide and N′-(2-cyanoacetyl)arylsulfonohydrazides. The scope and limitation of the method are demonstrated. The antibacterial and antifungal activities of the synthesized compounds were also evaluated.

Crystal structure of the triphenyltin(IV) chloride dimethyl N-cyanodithioiminocarbonate adduct

Abstract Reaction of dimethyl N-cyanodithioiminocarbonate, NCNC(SCH3)2 (L), and SnPh3Cl led to the formation of [ClPh3SnNCNC(SCH3)2] (1) which crystallizes in the monoclinic space group C2/c with Z=8, a=19.152(2) Å, b=12.8659 (16) Å, c=19.063(3) Å, β=108.608(3) and V=4451.6(10) Å3. The structure of 1 consists of a SnPh3 moiety trans-coordinated in apical positions by one L ligand, N-coordinated, and one chlorine atom involving a trigonal bipyramid geometry around the Sn(IV) atom. To our knowledge, this is the first isolation of a discrete triorganotin(IV) complex with a N-cyanodithioiminocarbonate adduct. The structural characterization of 1 was completed by infrared and nuclear magnetic resonance spectroscopy, and elemental analysis which confirm the X-ray elucidation.

Application of dimethyl N-cyanodithioiminocarbonate in synthesis of fused heterocycles and in biological chemistry

Abstract The synthetic chemistry of dimethyl N-cyanodithioiminocarbonate is reviewed. The scope and limitation of the most important approaches are discussed.

Recent trends in synthesis of five- and six-membered heterocycles using dimethyl N-cyanodithioiminocarbonate

Abstract New approaches to synthesis of five- and six-membered heterocyclic compounds utilizing dimethyl N-cyanodithioiminocarbonate are surveyed. The scope and limitation of the most important approaches are discussed.

Synthesis of Heavily Substituted 2-Aminopyridines by Displacement of a 6-Methylsulfinyl Group

2-Aminopyridines, with a variety of polar 6-substituents, were elaborated by displacement of a methylsulfinyl group from the 6-position of the pyridine ring. The requisite 6-thiomethyl pyridines were synthesized by reaction of 2-(1-phenylethylidene)propanedinitriles with dimethyl N-cyanodithioiminocarbonate.

First Synthesis of N‐Substituted Amino and N‐Sulfonylaminated Methylthiopyrimidines: Reaction of Dimethyl N‐Cyanodithioiminocarbonate with Substituted Hydrazides.

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A Novel Synthesis of N‐Aryl‐6‐methylsulfanyl‐4‐pyrimidinones and Purine Analogues: The Reaction of Dimethyl N‐Cyanodithioiminocarbonate with Cyanoacetanilides.

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A Novel Synthesis of N-Aryl-6-methylsulfanyl-4-pyrimidinones and Purine Analogues: The Reaction of Dimethyl N-Cyanodithioiminocarbonate with Cyanoacetanilides

A novel and efficient method for the synthesis of N-aryl-6-methylsulfanyl-4-oxopyrimidine-5-carbonitriles via the reaction of dimethyl N-cyanodithioiminocarbonate with substituted cyanoacetanilides has been investigated. (3)N-Aryl-2,5-diamino-7H-pyrazolo[3,4-d]-pyrimidin-4(3H)-one have also been prepared from the reaction of 6-sulfanylthio-N-aryl-4-pyrimidinones with hydrazines.

The Reaction of Dimethyl N-cyanodithioiminocarbonate with Amino- and Oxo-azoles: A New General Synthesis of Methylsulfanylazoloazines

A novel and efficient method for the synthesis of a new variety of methylsulfanylazoloazines by the reaction of dimethyl N-cyanodithioiminocarbonate with diazoles containing amino and active methylene functions. The synthetic potential of the method is demonstrated.

THE DESIGN AND SYNTHESIS OF STRUCTURALLY RELATED MERCAPTOPURINE ANALOGUES: REACTION OF DIMETHYL N-CYANO-DITHIOIMINOCARBONATE WITH 5-AMINOPYRAZOLES

A novel synthesis of 4-methylthiopyrazolo[1,5-a]-1,3,5-triazines via reaction of dimethyl N-cyanodithioiminocarbonate with 5-aminopyrazoles is reported and the synthetic potential of the method is demonstrated.