1,7-dithioxo systems. Reaction of 3-[(5,5-dimethyl-3-thioxocyclohex-1-en-1yl)sulfanyl]-5,5-dimethylcyclohex-2-ene-1-thione with 2-aminoethanol and ethane-1,2-diamine

The reaction of 3-[(5,5-dimethyl-3-thioxocyclohex-1-en-1-yl)sulfanyl]-5,5-dimethylcyclohex-2-ene-1-thione with 2-aminoethanol involves cleavage of the sulfide bond with formation of 3-[(2-hydroxyethyl)-amino]-5,5-dimethylcyclohex-2-ene-1-thione as the major product. The reaction of the same sulfide with ethane-1,2-diamine gave previously unknown 3-({2-[(5,5-dimethyl-3-thioxocyclohex-1-en-1-yl)amino]ethyl}-amino)-5,5-dimethylcyclohex-2-ene-1-thione.     

Studies in the benzazole and naphthazole series. VIII. Reaction of 2-hydrazinonaphth[1, 2-d]imidazole and its 1- and 3-methyl derivatives with carbon disulfide

When heated with carbon disulfide in pyridine 2-hydrazinonaphth[1, 2-d]imidazole yields S-triazolo[4, 3-b]-naphth[1, 2-d]imidazole-3-thione. Kinetic and not steric factors determine the formation of this compound. Its trans-angular structure is demonstrated by the agreement between its UV spectrum and that of 11-methyl-S-triazolo[4, 3-b]naphth[1, 2-d]imidazole-3-thione, prepared from 1-methyl-2-hydrazinonaphth[1, 2-d]imidazole and carbon disulfide, as well as by the identity of their methylation products. Methyl iodide methylation, in the presence of sodium methoxide, of S-triazolo[4, 3-b]naphth[1, 2-d]imidazole-3-thione, like that of S-triazolo[4, 3-a]benzimidazole-3-thione, takes place stepwise. First the methyl group adds to the nitrogen atom of the imidazole ring, and only then to the thiol group of the triazole ring.For Part VII see [3].     

Studies on organophosphorus compounds—XXVII: Synthesis of thiono-, thiolo- and dithiolactones

Unsubstituted and alkyl- or cyanosubstituted lactones such as dihydro-2(3 H)-furanone, dihydro-5-methyl-2(3 H)-furanone, dihydro-5,5-dimethyl-4-propyl-2(3 H)-furanone and tetrahydro-2,2-dimethyl-5-oxo-3furan-carbonitrile react with the dimer of p-methoxyphenylthionophosphine sulfide, 1, in anhydrous xylene or toluene to give the corresponding thionolactones, 3a-d, in good yields. Dihydro-2(3 H)-thiophenone and 1 produce dihydro-2(3 H)-thiophenthione. Aromatic lactones such as 2 H-1-benzopyran-2-one give the corresponding 2-thione. 1-Oxa-4-thiaspiro[4,5]decan-2-one, when treated with 1 at 120-125°, gave 1,4-dithiaspiro[4,5]decan-2-one and 1,4-dithias-piro[4,5]decan-2-thione. Tetrahydro-5,5-dimethyl-2-oxo-4-propyl-3-furancarboxylic acid ethyl ester reacted with 1 at 110° giving the corresponding 2-thione and 5,5-dimethyl-4-propyl-4,5-dihydrothieno[2,3-c]-1,2-dithiole-3-thione.     

Acylation of purine-8-thione and benzimidazole-2-thione: A reinvestigation of the site of acylation

Purine-8-thione ( 1 ) is acylated on nitrogen, not on sulfur as was previously reported. Thus, the reactions of 1 with ethyl chloroformate and with acetic anhydride yield, respectively, ethyl purine-8-thione-9( 7 )-carboxylate ( 3 ) and 9 ( 7 )acetylpurine-8-thione ( 7 ) as shown by independent synthesis and spectra. In like manner, benzimidazole-2-thione ( 10 ) reacts with acetic anhydride, ethyl chloroformate, benzoyl chloride, and cyclohexyl isocyanate to yield the corresponding N-acylated derivatives. In addition, 10 yields 1,3-dibenzoylbenzimidazole-2-thione on treatment with 2 equivalents of benzoyl chloride.     

Umsetzung von 3-(Dimethylamino)-2H-azirinen mit 1,3-Oxazolidin-2-thion zu 3-(2-Hydroxyethyl)-2-thiohydantoinen

Reaction of 3-(Dimethylamino)-2H-azirines with 1,3-Oxazolidine-2-thione to 3-(2-Hydroxyethyl)-2- thiohydantoins The reaction of 3-(dimethylamino)-2H-azirines 1 and 1,3-oxazolidine-2-thione ( 6 ), in MeCN at room temperature, yields, after hydrolytic workup, 3-(2-hydroxyethyl)-2-thiohydantoins 7 (Scheme 2). In the case of the spirocyclic 1c , crystallization of the crude reaction mixture leads to spiro [cyclopentane-1, 7′(7′aH)-imidazo [4, 3-b] oxazole] -5′-thione 8c . The mechanism is discussed.     

Sodium bis(2-methoxyethoxy)aluminum hydride in reactions with 3-cyano-6-methylpyridine-2(1H)-thione and 3-cyano-6-methyl(4,6-dimethyl)-2-methylthiopyridines

The reactions of sodium bis(2-methoxyethoxy)aluminum hydride with 3-cyano-6-methylpyridine-2(1H)-thione and 3-cyano-6-methyl-2-methylthiopyridine afforded 3-aminomethyl-6-methylpyridine-2(1H)-thione and azomethine of the pyridine series, respectively. The corresponding reaction with 3-cyano-4,6-dimethyl-2-methylthiopyridine gave rise to azomethine, substituted 3-aminomethylpyridine, and substituted dipyridylmethane.     

1-(2'-苯基-1', 2', 3'-三唑-4'-甲酰基)-4-芳基氨基硫脲及其 环化产物的合 成

以2-苯基-1,2,3-三唑-4-甲酰肼为原料合成了几种新的1-(2'-苯基-1',2',3'-三唑-4'-甲酰基)-4-芳基氨基硫脲,在不同条件下环化,制得一系列新的1,3,4-噻二唑、1,3,4-恶二唑和1,2,4-均三唑衍生物。化合物的结构经元素分析、IR、^1HNMR和MS确证,并对其波谱性质进行了讨论。     

Estimation of σ- and π-donor properties of heterocyclic thioamides by spectroscopic and magnetic resonance methods

The charge-transfer complexes (CTC) of few thioamide: 1-methylimidazoline-2-thione (MMI), 3-methyl-1-ethoxycarbonilimidazoline-2-thione (Carb), 5-methylbenzimidazoline-2-thione (BIZ), benzothiazoline-2-thione (BTZ), benzoxazoline-2-thione (BOZ) as σ-donors and diiodine as σ-acceptor were studied by spectroscopic methods (UV/Vis, (1)H NMR). CTC formation constants of thioamides with diiodine were determined using the function of the average-iodine number. The charge-transfer complexes of thioamides as π-donors with tetracyanoethylene (TCNE) as π-electron acceptor, were studied by UV-spectroscopy in dichloromethane and chloroform solutions. The mechanism of interaction MMI and Carb with TCNE have been studied by EPR spectroscopy. Spectral characteristics and formation constants are discussed in the terms of electron donor affinity of thioamides and the nature of the organic solvent used. The ionization potentials of donors were estimated from the CT transition energies of their complexes. The photolytic equilibrium constants of five thioamides are determined using pH-metric titrations.     

Reaction of azolethiones with diacetylene

Reactions of 2,3-dihydro-1H-benzimidazole-2-thione, 2,3-dihydro-1H-1,2,4-triazole-3-thione, 4-amino-5-phenyl-3,4-dihydro-2H-1,2,4-triazole, and 6-aminopurine-2-thiol with diacetylene in DMSO gave the corresponding 1-(azolylsulfanyl)but-1-en-3-ynes having Z configuration of the double bond.     

Studies on organophosphorus compounds—XLI : Formation of 3-pyrazoline-5-thione disulfides from 3,5-pyrazolidinediones. C-alkylation of 3,5-pyrazolidinediones

4-Substituted-1,2-diphenyl-3,5-pyrazolidinediones (Phenylbutazone analogous) 1a–d react with 2,4-bi-(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-difulside (Lawesson Reagent (LR) with formation of the corresponding 3,3′-dithiobis (1,2-dihydro-3H-pyrazole-5-thione)'s 2a–d. When the 4-substituent contains a sulfoxide group this is deoxygenated to the sulfide by LR at room tmeperature. 1-Phthalazinone-4-thione, 1,4-phthalazine-dithione and ethyl aminothioxoacetate have also been prepared from the corresponding carbonyl compounds. Alkylation or acylation of 2a–d yielded 3H-pyrazole-3-thione derivatives 8 and 9. Alkylation of 1 with MeI in the presence of Et₃N at room temp. yielded the C-alkylated products 10 exclusively. X-RAy crystallographic investigations of 2b and 9a are presented.     

Action of Nucleophilic Phosphorus Reagents on Heterocyclic cis-Disulfides

As a contribution to previous studies of the reaction of phosphorus nucleophiles with heterocyclic cis-disulfides,^1,2 the reactivity of trialkyl phosphites 2 toward 5-p-chlorophenyl-4-cyano-1,2-dithiol-3-thione 1a, 5-phenyl-1,2,4-dithiazol-3-thione 1b and its 3-carbonyl derivative 1c has now been investigated.     

The synthesis and spontaneous resolution of 2-(2-thioxothiazolidin-3-yl)thiazole

A single crystalline enantiomer of 2-(2-thioxothiazolidin-3-yl)thiazole 5 has been isolated as the major product of the pyrolysis of 3-(2-thiazolin-2-yl)thiazolidine-2-thione 3 (n = 1); the latter isolated as the sole product of the reaction between thiazolidine-2-thione 2 (n = 1) and diethyl azodicarboxylate (DEAD) in benzene.     

Synthesis of 4,5-dihydrothiazole derivatives by the reaction of perfluoro-2-methylpent-2-en-3-yl isothiocyanate with ambident N,O- and N,S-nucleophiles

The reactions of perfluoro-2-methylpent-2-en-3-yl isothiocyanate with ambident N,O- and N,S-nucleophiles (thiazole-2-thione, pyridine-2-thione, 2-hydroxypyridine, benzothiazole-2-thione, benzoxazole-2-thione, 3,4,5,6-tetrahydropyrimidine-2-thione) in the presence of triethylamine yield only 2-N-substituted 4,5-dihydrothiazole derivatives. The molecular structures of three products were determined by X-ray diffraction analysis. The reaction pathways are discussed.     

Luminescent silver nitrate complexes of bis[2-(diphenylphosphano)phenyl]ether (DPEphos): Crystal structure of [Ag(DPEphos)(py2SH)2]NO3

Heteroleptic silver(I) nitrate complexes containing the bis[2-(diphenylphosphano)phenyl]ether (DPEphos) ligand and the heterocyclic thioamides pyridine-2(1H)-thione (py2SH), pyrimidine-2(1H)-thione (pymtH), 4,6-dimethylpyrimidine-2(1H)-thione (dmpymtH), 1,4,5,6-tetrahydropyrimidine-2-thione (thpymtH) or 1,3-imidazolidine-2-thione (imtH₂) have been synthesized and characterized by IR and UV-Vis spectroscopy, elemental analyses and melting point determinations. The complexes can be obtained by the addition of the thioamide ligand to an AgNO₃-diphosphane adduct in dichloromethane/ethanol solution. The molecular structure of [Ag(DPEphos)(py2SH)₂]NO₃ complex has been established by single-crystal X-ray diffraction. The structure features a tetrahedral silver(I) center with two phosphorus atoms from the chelating diphos ligand, and the exocyclic sulfur atom of two heterocyclic thioamide units. Intense blue-green emission is observed in the region 470-483 nm for all the complexes in the solid state and in solution at ambient temperature.     

Photodegradation kinetics of some thiols and thiones in aqueous suspension of zinc oxide

Photodegradation of several thiols and thiones including 2-pyrimidinethiol, thiazolidine-2-thione, imidazolidine-2-thione, 1,2,4- triazole 3-thiol and 2,5-dimercapto- 1,3,4-thiadiazole have been studied in aerated aqueous solution using zinc oxide under irradiation with 400W high pressure mercury lamp. Rate constants span the range from 2.44 x 10(-2) min x (-1) to 1.76 x 10(-1) min x (-1). The slower degradation rate of 2-imidazoline 2-thione could be related to oxidation potential of the corresponding ring. The Langmuir-Hinshelwood (L-H) rate constant k(r) and adsorption constant, (KA) for all five thiols and thiones are reported.     

Identification of indoline-2-thione analogs as novel potent inhibitors of α-melanocyte stimulating hormone induced melanogenesis

Based on the hits, 3,4-dihydroquinazoline-2-thione (1) and benzimidazole-2-thione (2), a series of indole-2-thione (3) and indole-2-thiol inhibitors (4) of melanogenesis were designed, synthesized and evaluated in melanoma B16 cells under the stimulant of α-melanocyte stimulating hormone (α-MSH). The indole-2-thione compounds (3a-g) exhibited an effective inhibitory activity on melanin synthesis. The Structure-Activity Relationship (SAR) studies of 2 have revealed that in potent inhibitor 3a (>100% inhibition at 30 μM, IC50=1.40 μM) the role of nitrogen (3-N) at 3-position is insignificance. In addition, the hydrophobic substituents of 3 were better than the hydrophilic one. However, conversion of thione (-C=S, 3) to thiol (-C-SH, 4) led to decrease in the potency.     

The synthesis of imidazole-2-thione nucleosides

Ribosylation of the trimethylsilyl derivative ( 1b ) of imidazole-2-thione ( 1a ) using either stannic chloride or silver perchlorate as catalyst resulted in the formation of the acylated derivatives of 1-(β-D-ribofuranosyl)imidazole-2-thione ( 3c ) and 1,3-di-(β-D-ribofuranosyl)imidazole-2-thione ( 4c ) with the latter predominating ( 4c:3c , ca. 2:1 ). The diribosylated nucleoside 4c was shown to be the N,N-disubstituted product rather than the N,S-disubstituted product by ¹H nmr and ¹³C nmr spectroscopy. Employment of the iodine-catalyzed fusion procedure reversed the aforementioned product ratios and provided the monoriboside 3c in excellent yield. When the trimethylsilyl derivative ( 5b ) of 2-methylthioimidazole ( 5a ) was reacted with 2,3,5-tri-O-benzoyl-D-ribofuranosyl bromide ( 2d ) in acetonitrile, the major product was 1,3-di-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-imidazole-2-thione ( 4b ). The formation of 4b in this reaction is thought to arise via the Hilbert-Johnson mechanism.     

Synthesis in the phenothiazine series

The corresponding amines were obtained by reduction of 1-nitro-3-bromophenothiazine and 2-bromo-4-nitrophenothiazine. 1-Amino-3-bromophenothiazine reacts with formic acid to give 4-bromoimidazo[4,5,1-k, l ]phenothiazine and with carbon disulfide to give 4-bromo-1,2-dihydroimidazo [4,5,1-k, l ]phenothiazine-1-thione. 4-Aminophenothiazine reacts with sulfur and carbon disulfide to give 2, 3-dihydrothiazolo[5,4-c]phenothiazine-2-thione.See [1] for communication XXXIV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 202–203, February, 1974.     

The synthesis of compounds with antithyroid activity

N-Acyl derivatives of imidazole-2-thione and its derivatives were obtained by the reaction of imidazole2-thione and its derivatives with aliphatic anhydrides and with benzoyl chloride in pyridine. The hydrochlorides of 1-methyl and 4 (5)-methyl-S benzoylimidazole-2-thione were obtained by the reaction of 1-methyl- and 4 (5)-methylimidazole-2-thione with benzoyl chloride in dry ethanol. The acylation of imidazole-2-thione and of some of its derivatives was investigated with the aid of their IR spectra, and the importance of the medium in the formation of N- and S -acyl derivatives was shown, as well as the possibility of the migration of substituants from the S — to the N atom under its influence.For part VI see [1].     

Adamantylazoles: X. Reactions of 1,2,4-Triazole-3-thione with 1-Adamantanol in Acid Solutions

1,2,4-Triazole-3-thione reacts with 1-adamantanol in concentrated sulfuric acid to form 1-(1-adamantyl)-1,2,4-triazole-3-thione, which transforms into 1-(1-adamantyl)-3-(1-adamantyl)sulfanyl-1,2,4-triazole or is oxidized with atmospheric oxygen dissolved in sulfuric acid into 3,3′-disulfanediylbis[1-(1-adamantyl)- 1,2,4-triazole]. 3-(1-Adamantyl)sulfanyl-1,2,4-triazole was prepared by adamantylation of 1,2,4-triazole-3-thione in a mixture of phosphoric and acetic acid (weight ratio 4 : 1).