Thiocarbamoyl Group Research Articles

Cyanothioacetamides as a synthetic platform for the synthesis of aminopyrazole derivatives.

It was shown that the reaction of 2-cyanothioacetamides with hydrazine involves both cyano- and thioamide groups, and 3,5-diaminopyrazoles are formed. In the reaction of 2-cyano-3-(dimethylamino)-N,N-dimethylprop-2-enethioamides with hydrazine and its derivatives, the interaction proceeds with the participation of cyano- and enamine groups, not affecting the thiocarbamoyl group, and leads to the formation of 4-thiocarbamoylpyrazoles. A synthesis method has been developed and a series of 1-substituted-4-thiocarbamoyl pyrazoles has been thus synthesized. The structure of the reaction products was studied using NMR spectroscopy and mass spectrometry and confirmed by X-ray diffraction analysis.

Novel Benzimidazole Derivatives: Cytotoxic and Apoptotic Properties on Lung Cancer Cell Line

Background: Benzimidazole derivatives are privileged molecules known to have a wide variety of biological activities. In medicinal chemistry, due to the ring’s structural similarity to nucleotides, its derivatives were investigated as new chemotherapeutic agents. Our research group have been studying 1,2-disubstituted benzimidazoles, including thiocarbamoyl group and their potential anticancer activity. Based on previous findings, we synthesized novel 1-[2-(4-substituted phenyl-2-oxoethyl)]-2-[(2/3/4-substituted phenylpiperidin-1-yl)thiocarbamoyl]benzimidazole derivatives (3a-o). Methods: The obtained fifteen derivatives were studied on A549 adenocarcinomic human alveolar basal epithelial cell line and mouse L929 fibroblastic cell line to determine their cytotoxic activity. These compounds were also investigated to identify their apoptotic properties. Results and Discussion: The structures of the compounds based on three different groups differ from each other with the phenyl substituents bonded to the piperazine ring. All of the compounds showed remarkable antitumor activity, but the first five compounds bearing non-substituted phenyl moiety exhibited selective cytotoxicity when compared in terms of potencies to the normal cell line. Conclusion: Compounds 3j, 3m and 3n were identified as the most apoptotic derivatives; however, compounds 3e and 3h provoked apoptosis with the percentages of 10.6 and 10.9% and selective cytotoxicity.

Synthesis, physico-chemical studies and biological evaluation of new metal complexes with some pyrazolone derivatives

A series of N-substituted-4-thiocarbamoyl-5-pyrazolone derivatives (HL1-HL4) is presented as chelating agents for complexation with Fe(III), Ni(II) and Cu(II) metal ions. The synthesized pyrazolone ligands and their newly metal complexes are characterized by different spectral and analytical methods such as UV–Vis, IR, 1H NMR, 13C NMR, ESR, MS, magnetic measurement, and TGA. The spectral data reveal that ligands coordinated to metal ions in a bidentate pattern via O & N atoms of the OH group at C(5) and thiocarbamoyl (–CSNHR) at C(4) of the pyrazolone ring. Also, the analytical data suggest the stoichiometries 2:3 (M:L) for both Cu(II) & Ni(II) complexes and 1:3 for Fe(III) complexes. Besides, the normal magnetic moments values for Fe(III) complexes confirm high spin octahedral structure while the diamagnetic nature of all Ni(II) complexes is consistent with square planar geometry. However, the subnormal magnetic values for Cu(II) complexes suggest the proposal of their binuclear structures. The ESR spectra of the Cu(II) complexes support the distorted square planar geometry with a considerably strong intradimeric spin-exchange interaction. Moreover, the anticancer, antibacterial and antifungal activities are screened. Among the synthesized compounds, HL4 ligand exhibits a significant broad spectrum of action against Gram-positive (S. aureus), Gram-negative bacteria (P. vulgaris), and antifungal potency against A. fumigatus &C. albicans in comparison with gentamicin and ketoconazole drug. Such potency of HL4 could be related to the insertion of the p-chloro in the phenyl group attached to the pharmacophoric thiocarbamoyl group at C(4). Furthermore, IC50 values of two Cu(II) complexes derived from HL2 and HL3 display nearly twofold or threefold more cytotoxicity impact against three cell lines (MCF-7, HCT116 and HepG-2) compared with cis-platin as positive control.

Chemical modification of polyvinyl chloride with thiourea

The quasi-homogeneous (“synthesis in gel”) conditions for functionalization of polyvinyl chloride (PVC) with thiourea were experimentally selected. It was found that the best solvent for the formation of PVC gel is DMF, ensuring formation of the gel in the range of polymer concentrations from 10 to 30%. The composition of the products was characterized by elemental analysis data, the specific features of their structure were established by Fourier-transform IR spectroscopy and thermogravimetry. It was shown that thiourea reacted with PVC as an N-nucleophile to form thiocarbamoyl groups in the polymer structure. The maximum achieved total degree of functionalization was 0.31. The reaction was accompanied by cross-linking and partial dehydrochlorination.

Octacarbamoylated and octathiocarbamoylated resorcinarenes: transformations and acceptor properties

A series of octa(thio)carbamoylated resorcinarenes was synthesized by the reactions of rccc-resorcinarenes with N,N-dimethylcarbamoyl and N,N-dimethylthiocarbamoyl chlorides in the presence of alkali carbonates. The derivatives with thiocarbamoyl groups were transformed into octa(carbamoylthio)resorcinarenes by the thione—thiol rearrangement. In a homogeneous medium octacarbamoylated resorcinarenes demonstrated high acceptor properties and selectivity to cesium cations but manifested low extraction ability towards alkali metal cations from the aqueous phase to organic one because of the formation of stable films at the interface. Resorcinarenes with thiocarbamoyl and carbamoylthio groups are capable of extracting lanthanides (Nd3+, Yb3+) from aqueous media and are selective to Nd3+ cations.

Design, Synthesis and Antibacterial Evaluation of Some New Pyrazolinyl Bromophenylthiazoles

In this study a stepwise reaction has been designed for the synthesis of some new derivatives of Pyrazolinyl bromophenylthiazoles. The progress started by the benzylation of 2,4-dihydroxyacetophenone to give 1-[2,4-bis(4-chlorobenzyloxy)phenyl]ethanone (1) which was reacted with a number of benzaldehydes to produce a series of new α,β-unsaturated carbonyl compounds (2a-j). Followed by Michael addition with thiosemicarbazide affording new pyrazolines bearing thiocarbamoyl group(3a-j). A later derivatives were treated with 4-bromophenacyl-bromide yielding a series of a target pyrazolines having a thiazole linkages(4a-j).The final products were screened for their antimicrobial evaluations using micro broth dilution method against S.aureus as gram positive and E.Coli as gram negative.Spectroscopic techniques were utilized to elucidate the structures of the prepared compounds.

Synthesis and Characterization of Some New 4,5-Dihydropyrazolyl Thiazoles

The prepared starting material 2,4-bis (4-chlorobenzyloxy)acetophenone (1) has been reacted with different substituted benzaldehydes to give a series of new chalcones (2a-j). The prepared new chalcones were subjected to react with thiosemicarbazide according to the Michael addition reaction to afford new thiocarbamoylpyrazoline derivatives (3a-j). A thiocarbamoyl group in compounds (3a-j) was cyclized with p-bromophenacyl bromide to give a series of new 4,5-dihydropyrazolyl thiazoles (4a-j). The structures of the synthesized compounds were characterized by spectral methods: FT-IR, 1 H-NMR, 13 C-NMR and DEPT-135 spectra.

ChemInform Abstract: Synthesis of N,N‐Dialkyl‐9‐oxoacridine‐10(9H)‐carbothioamides via the Reaction of (2‐Halophenyl)(2‐isothiocyanatophenyl)methanones with Secondary Amines, Followed by Cyclization with NaH.

The first preparation of acridin-9(10H)-ones carrying a tertiary thiocarbamoyl group at C(10), i.e., N,N-dialkyl-9-oxoacridine-10(9H)-carbothioamides 9, is described. The method is based on the reaction of (2-halophenyl)(2-isothiocyanatophenyl)methanones 7, prepared from (2-aminophenyl)(2-halophenyl)methanones 5 by a convenient three-step sequence, with secondary amines in DMF at room temperature to generate the corresponding thiourea derivatives 8 in situ, which are treated with NaH at 100–120° to provide the desired products in one-pot reactions in generally good yields.

Synthesis of N,N‐Dialkyl‐9‐oxoacridine‐10(9H)‐carbothioamides via the Reaction of (2‐Halophenyl)(2‐isothiocyanatophenyl)methanones with Secondary Amines, Followed by Cyclization with NaH

AbstractThe first preparation of acridin‐9(10H)‐ones carrying a tertiary thiocarbamoyl group at C(10), i.e., N,N‐dialkyl‐9‐oxoacridine‐10(9H)‐carbothioamides 9, is described. The method is based on the reaction of (2‐halophenyl)(2‐isothiocyanatophenyl)methanones 7, prepared from (2‐aminophenyl)(2‐halophenyl)methanones 5 by a convenient three‐step sequence, with secondary amines in DMF at room temperature to generate the corresponding thiourea derivatives 8 in situ, which are treated with NaH at 100–120° to provide the desired products in one‐pot reactions in generally good yields.

Directed ortho-metalation versus reductive amination in the preparation of polytopic, highly substituted, and sterically congested amine-S-arylthiocarbamates as thiophenol precursors

The synthesis of polydentate amine-S-arythiocarbamates was tested by directed ortho-lithiation of 2,4-disubstituted thiophenols, or the corresponding O- and S-arylthiocarbamates by deprotonation or lithium–bromine exchange, followed by addition of the electrophiles N(CH2CH2X)3 (X=Br, I). In the case of the thiophenol, deprotonation resulted in a trithioether-amine upon addition of the electrophile. With the O- and S-thiocarbamates, the reactions resulted in the migration of the thiocarbamoyl group to the ortho-position (Fries rearrangement), or nucleophilic attack of the carbonyl group by butyllithium, respectively. An alternative route employed 2,4-disubstituted phenols to obtain the corresponding salicylaldehydes, and subsequently the O-arylthiocarbamates for Newman–Kwart thermal rearrangement (NKR). Finally, the formyl group on the S-arylthiocarbamates allowed reductive amination to assemble polytopic compounds with amine and S-thiocarbamate groups.

Cyanothioacetanilide Intermediates in Heterocyclic Synthesis, Part 1: Synthesis and Biological Evaluation of Some Novel Thiazole, Thiophene, Pyrazole, and Pyrazolo[1,5-a]Pyrimidine Derivatives

Some novel thiophenes (4a,b, 5, and 9a,b) were obtained from the cycloalkylation of the thiocarbamoyl group in the cyanothioacetanilide derivative (1) with α-halocarbonyl compounds. Also, the reaction of cyanothioacetanilide derivative with phenyl isothiocyanate in the presence of potassium hydroxide followed by in situ heterocyclization of the resulting adduct with α-halocarbonyl compounds furnished the corresponding thiazole (12, 14, and 15), pyrazole (19), and pyraozlo[1,5-a]pyrimidine (22, 25, and 26) derivatives. Compounds (4b, 5, 9a, 12, 13, 18, 22, 25, and 26) were tested to evaluate their antimicrobial activity. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.

Bis-pyrazolines: Synthesis, characterization and antiamoebic activity as inhibitors of growth of Entamoeba histolytica

The cyclization of chalcone with N-4 substituted thiosemicarbazides under basic condition led to the formation of new compounds, thiocarbamoyl bis-pyrazoline derivatives. The structure of the compounds were elucidated by UV, IR, 1H NMR, 13C NMR and ESI-MS spectral data and thermogravimetric analysis, and their purities were confirmed by elemental analyses. The antiamoebic activity of these complexes was evaluated by microdilution method against HM1: IMSS strain of Entamoeba histolytica and the results were compared with the standard drug, metronidazole. Structure–activity relationship shows that the compound with aromatic substituents at the thiocarbamoyl group was more active than those with the cyclic groups. However, it was clear from the IC 50 values that the compounds 15 and 20 are more active and both showed a structural resemblance having an electron withdrawing groups attached to the phenyl ring. MTT assay showed that all the compounds are non-toxic to human kidney epithelial cell line.

Competing processes in the condensation of diethyl ethoxymethylidenemalonate and malononitrile derivatives with CH acids containing a thiocarbamoyl group

Diethyl ethoxymethylidenemalonate and ethoxymethylidenemalononitrile react with CH acids containing a thiocarbamoyl group along several concurrent pathways to give both acyclic structures and pyridine and pyrimidine derivatives.

Synthesis and Fluorescent Properties of Bi- and Tricyclic 4-N-Carbamoyldeoxycytidine Derivatives

New bi- and tricyclic deoxycytidine derivatives (dChpd, dCmpp, dCtpp, dCppp) were synthesized as analogues of a fluorescent nucleoside, dChpp, previously reported. The carbamoyl group of dChpd and the 5-position of the cytosine ring are bridged via an ethylene linker so that the modified group forms a nonplanar structure with the cytosine ring. The fluorescent study of dChpd indicated that the coplanar structure between the carbamoyl group and the cytosine ring is of importance. N-Methylation of the carbamoyl group (dCmpp) weakened the intensity of the fluorescence of dChpp, and the derivative (dCtpp), which had a thiocarbamoyl group, lost its fluorescent property. Moreover, addition of a pyrrolo-ring (dCppp) to dChpp enhanced the intensity of fluorescence, and an emission light was observed with a marked Stokes shift of 120 nm.

Fluorescent oxidation products derived from DBD-thiocarbamoyl amino acid in the modified Edman sequencing analysis.

The fluorescent product obtained by the oxidation of 7-N, N-dimethylaminosulfonyl-4-(2,1,3-benzoxadiazolyl) (DBD)-thiocarbamoyl (TC)-proline with NaNO(2)/H(+) in the modified Edman sequencing procedure was identified as the corresponding thiazolyl compound, N-[(8-dimethylaminosulfonyl)thiazolo[5,4, e]benzo[2,1,3]oxadiazol-5-yl]-L-proline, formed by the attack of the sulfur atom of the thiocarbamoyl group on the benzofurazan skeleton. The reaction mechanism for the formation of the fluorescent compound from DBD-TC primary and secondary amines is also discussed.

>5-Benzylidene-8-ethylthiocarbamoyl-9-phenyl-7,8-diazabicyclo[4.3.0]non-6-ene

The title compound, C23H25N3S, was obtained by the reaction of dibenzylidene cyclohexanone with hydrazine hydrate, followed by the treatment of the resulting pyrazoline compound with ethylisothiocyanate. The structure of the title compound was elucidated by IR, 1H-NMR spectroscopy and elementary analysis, and the stereochemical properties were investigated by X-ray analysis. The cyclohexane ring has a slightly distorted chair conformation while the 2-pyrazoline system is highly flattened from an ideal envelope conformation. One phenyl ring and thiocarbamoyl group are linked to the 2-pyrazoline system in axial and in equatorial positions, respectively. The other phenyl ring is bonded to the exocyclic double bond.

NEW COMPLEXES OF PALLADIUM(II) CHLORIDE WITH CHELATING PHOSPHORUS, SULFUR CONTAINING LIGANDS

Abstract New palladium(II) coordination compounds PdLCl2 and PdL2Cl2 with chelating ligands containing thiophosphoryl groups along with carbamoyl or thiocarbamoyl groups were synthesized. The structures of the complexes in solutions and in solid were studied by electronic and IR spectroscopy, conductometry, and FD mass spectrometry. Transformations of the complex PdL3 2Cl2 under a strong electric field were investigated.

Synthesis of ethoxycarbonyl-1,4- and -1,2-dihydropyridinecarboxylic acid amides

3-Carbamoyl derivatives of 4-phenyl-5-ethoxycarbonyl-2,6-dimethyl-1,4-dihydropyridine were obtained by cyclocondensation of 2-benzylideneacetoacetic ester with Β-aminocrotonic acid amide or anilides. In the alkylation of 4-phenyl-5-ethoxycarbonyl-2,6-dimethyl-1,4-dihydropyridine-3-carboxylic acid anilides the amido group is initially alkylated, after which the ring NH group is alkylated, while the thiocarbamoyl group is converted to a cyano group. Reduction of the pyridinium salts gave 3- and 5-carbamoyl derivatives of 4-phenyl-1,2,6-trimethyl-1,2-dihydropyridine-5- and -3-carboxylic acids.

Synthesis of Methyl 2‐Acetamido‐4,6‐di‐O‐acetyl‐3‐S‐acetyl‐2‐deoxy‐3‐thio‐α‐D‐mannopyranoside

AbstractMethyl‐2‐acetamido‐4,6‐di‐O‐acetyl‐3‐S‐acetyl‐2‐deoxy‐3‐thio‐α‐D‐mannopy‐ranoside has been synthesized by conversion of methyl 2‐amino‐2‐deoxy‐4,6‐O‐benzylidene‐α‐D‐altropyranoside into the corresponding 3‐O‐methanesulfony1‐2‐N‐[(methylthio)thiocarbonyl]derivative followed by intramolecular displacement of the 3‐O‐methanesulfonyloxy group with the (methylthio)thiocarbamoyl group.