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A novel, high-yielding, one-step synthesis of 2-chloroquinazolin-4-ols and analogous bicycles from 2-aminoamides using thiophosgene is described. The scope of the reaction includes aminothioamides, amino acids, and fused heterocycle derivatives, furnishing quinazolines, oxazinones, and substituted fused pyrimidine bicycles, respectively. On the basis of observed results with substituted analogues, a mechanism for this transformation is thought to occur via an isothiocyanate intermediate followed by an unexpected chemoselective reaction of thiophosgene on the thiol intermediate.

In this article, we report the photophysical and biological properties of new luminescent rhenium(I) polypyridine fluorous complexes. The complexes [Re(N∧N)(CO)3(py-Rf-NH2)](PF6) (py-Rf-NH2 = 3-amino-5-(N-((3-perfluorooctyl)propyl)aminocarbonyl)pyridine; N∧N = 1,10-phenanthroline (phen) (1a), 3,4,7,8-tetramethyl-1,10-phenanthroline (Me4-phen) (2a), 4,7-diphenyl-1,10-phenanthroline (Ph2-phen) (3a)) contain a fluorous pendant and a primary amine for modification. They have been converted to the isothiocyanate complexes [Re(N∧N)(CO)3(py-Rf-NCS)](PF6) (py-Rf-NCS = 3-isothiocyanato-5-(N-((3-perfluorooctyl)propyl)aminocarbonyl)pyridine; N∧N = phen (1b), Me4-phen (2b), Ph2-phen (3b)) with thiophosgene. The isothiocyanate complexes have been reacted with ethylamine, a model substrate, yielding the thiourea complexes [Re(N∧N)(CO)3(py-Rf-TU-Et)](PF6) (py-Rf-TU-Et = 3-ethylthioureidyl-5-(N-((3-perfluorooctyl)propyl)aminocarbonyl)pyridine; N∧N = phen (1c), Me4-phen (2c), Ph2-phen (3c)). Upon irradiation, all of these...

In this work, we described the synthesis of 3-isothiocyanatoselenophenes starting from 3-aminoselenophenes (using thiophosgene). Those compounds were then converted to the corresponding thioureas in the presence of ammonium hydroxide. Cyclization in 2-aminoselenolo[3,2-d]thiazoles was achieved using DDQ. 2-Aminothieno[3,2-d]thiazoles were obtained from 3-isothiocyanatothiophenes using the same pathway.

A sequential one-pot synthesis of N-sulfonylcyclothioureas from N-monosulfonyl diamines, CS2 and chloroacetic acid at room temperature in water is described. In the absence of highly toxic thiophosgene and organic solvents, this method is environmentally benign. Simple reaction conditions, easy purification of the products, good yields and thioglycolic acid as the useful byproduct are also important attributes of this methodology. The plausible mechanism including tandem reactions is proposed.

The reactive nitroxides 2,2,6,6-tetramethyl-1-oxyl-4-piperidyl chloroformate and 2,2,6,6-tetramethyl- 1-oxyl-4-piperidyl chlorothionoformate were synthesized from 2,2,6,6-tetramethyl-4-hydroxypiperidin- 1-oxyl and diphosgene (68%) or thiophosgene (61%), respectively. The reactions of the chloroformate and chlorothionoformate with lower secondary amines lead to 2,2,6,6-tetramethyl- 1-oxyl-4-piperidyl N,N-dialkylcarbamates (59 - 94%) and thionocarbamates (35 - 65%), respectively. Unexpectedly, the same 2,2,6,6-tetramethyl-1-oxyl-4-piperidyl N,N-dialkylcarbamates were obtained directly in a one-pot reaction of 2,2,6,6-tetramethyl-4-hydroxypiperidin-1-oxyl with diphosgene and lower tertiary alkylamines by dealkylation in 32 - 86% yield. The antifungal activity of the synthesized carbamates and thionocarbamates has been demonstrated

A novel synthesis of different aromatic and heteroaromatic difluorodioxole derivatives has been developed. The starting materials were catechols, which, after treatment with thiophosgene, formed at 0 °C the respective thiodioxoles. The latter were reacted for a short time with commercially available bromine trifluoride, producing potentially biologically important difluoroaryldioxoles in moderate to high yields.

This contribution studies the decomposition of folpet fungicide under oxidative conditions and compares the product species with those of captan fungicide, which is structurally related to folpet. Toxic products arising from folpet comprised carbon disulfide (highest emission factor of 4.9 mg g(-1) folpet), thiophosgene (14.4), phosgene (34.1), hydrogen cyanide (2.6), tetrachloroethylene (111), hexachloroethane (167), and benzonitrile (4.5). Owing to their related molecular structures, folpet emitted similar products to captan but at different yields, under the same experimental conditions. It appears that the availability of easily abstractable H atoms, in the structure of captan but not in that of folpet, defines the product distribution. In conjunction with the quantum chemical calculations, these experimental measurements afford an enhanced explanation of the formation pathways of hazardous decomposition products of these two structurally related fungicides.

A calculation of the rate of ISC (intersystem crossing) relaxation at 0 K requires a knowledge of the spin–orbit coupling and the vibrational overlap integrals (Franck-Condon factors) between the T1 and S0 states. At elevated temperatures, the population of the rotational states needs to be taken into account through the overlap of the rotational wavefunctions between the interacting T1/S0 electronic states. Here, we discuss the effect of the ISC singlet–triplet selection rules on the number and magnitude of the rotational overlap factors for the J = 0, 5, and 10 rotational levels of thiophosgene, Cl2CS. Of equal importance is the influence of the spin–spin and spin-rotation coupling on the rotational fragmentation factors and the ISC survival probability. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011

The amorphous, brownish black substance obtained by Dewar and Jones from nickel carbonyl and thiophosgene, has not the composition (CS)x but contains organically combined chlorine. The reaction has been carried out in various solvents; the amorphous reaction products have been completely analysed and it appears that the solid adsorbs the solvent, which cannot be completely removed. The C: S ratio in these products therefore varies from 1: 0.8 to 1: 0.9. The reaction was also carried out in the vapour phase. The amorphous product so obtained also contained organically combined chlorine while the C:S ratio was 1: 1.03 in this case. Thus the product produced from nickel carbonyl and thiophosgene is not a polymeric form of carbon monosulphide.

During a study of thiophosgene electronic spectra, Fujiwara and co-workers observed a broad electronic transition peaked at 37 000 cm −1 , attributed to thiophosgene dimer. Our dispersed fluorescence spectra of a thiophosgene molecular beam excited at 36 000 cm −1 reveal several vibrational modes too low in frequency for thiophosgene. We assign them to modes of thiophosgene dimer or their combination bands. MP2 calculations support the vibrational assignment. TD-DFT, CASSCF, and coupled cluster calculations suggest that the bright electronic state of thiophosgene dimer is the B 2u symmetry fifth excited singlet state. Two additional transitions are assigned to a thiophosgene synthesis impurity, trichloromethanesulfenyl chloride.

Isothiocyanates having the NCS-group bound directly to the CC-bond — the vinyl isothiocyanates — are of high synthetic interest because this type of heterodienes is a suitable precursor for heterocyclic compounds and derivatives of thiocarbamic acid. They cannot be prepared by standard methods. In this review we report 1) the synthesis of vinyl isothiocyanates by the reaction of nitrogen compounds with thiophosgene and other sulphur compounds, SNV-reactions, elimination of HX, addition of HSCN to alkynes, cleavage of heterocycles and by miscellaneous methods 2) structure and reactivity of the vinyl isothiocyanates and 3) the reactions of these conjugated mustard oils with numerous nucleophiles and their behaviour as heterocumulenes in cycloaddition reactions.

Thiophosgene (Cl2CS) is a favorite model system for studies of photophysics, vibrational dynamics, and intersystem interaction effects. But there are no previous rotationally-resolved infrared studies because the spectra are very congested due to hot bands and multiple isotopic species. This paper reports a detailed study of the ν2 (not, vert, similar504 cm−1) and ν4 (not, vert, similar471 cm−1) fundamental bands for the two most abundant isotopomers, 35Cl2CS and 35Cl37ClCS, based on spectra with observed line widths of not, vert, similar0.0008 cm−1 obtained at the Canadian Light Source far-infrared beamline using synchrotron radiation and a Bruker IFS125 Fourier transform spectrometer.

Thio and seleno analogs of fenuron, isoproturon, chlorotoluron, metoxuron, monuron, and diuron were synthesized from the corresponding aryl amines. Their reaction with thiophosgene leads to isothiocyanates. Aryl amines were also converted (via isocyanides) to isoselenocyanates. The reaction of both isothio- and isoselenocyanates with dimethylamine affords the corresponding thio and seleno analogs of the above-mentioned urea herbicides. Herbicidal activity of the synthesized compounds was slightly lower than the activity of the parent urea herbicides. The thio and seleno analogs as well as the parent ureas showed good fungicidal activity at a concentration of 200 ppm against selected fungi.

A novel series of optically active 2-aminobenzothiazole derivatives were synthesized by reaction of optically active amine (I) with thiophosgene to obtain optically active isothiocyanates (IIa-h) which on condensation with 4-fluoro-3-chloro aniline (III) yielded various optically active thioureas (IVa-h). Further oxidative cyclisation in the presence of bromine and chloroform yielded title compounds (Va-h). The structures of these compounds were established by IR, (1)H NMR, (13)C NMR, Mass and HRMS. The compounds (IVa-h and Va-h) were evaluated for in vitro cytotoxicity against mouse Ehrlich Ascites Carcinoma (EAC) and two human cancer cell lines (MCF-7 and HeLa). In preliminary MTT [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide] cytotoxicity studies the optically active thiourea derivatives (IVe, IVf and IVh) were found most effective. In EAC cells the IC(50) values for IVe, IVf, IVh and Vg were found in the range of 10-24 microM, whereas in MCF-7 and HeLa cells the IC(50) values were observed in the range of 15-30 microM and 33-48 microM, respectively. In alkaline comet assay the compounds (IVe and IVf) showed dose-dependent DNA damaging activity.

1,2-cis-Fused bicyclic sugar thiocarbamates of gluco and manno configurations have been prepared by treatment of the corresponding O-unprotected amino sugars and glycopyranosyl amines with thiophosgene. The reactivity of these compounds towards amines has been studied in order to determine whether these compounds could act as latent isothiocyanates; it is shown that 1,2-cis-fused bicyclic sugar thiocarbamates are more stable than their trans analogues, and are not transformed into thioureas upon treatment with amines. An unprecedented isomerization of a peracetylated glucopyranoso[2,1-d]oxazolidine-2-thione into a glucopyranoso[2,1-d]thiazolidin-2-one in DMF is also reported. The structure of this thiazolidin-2-one was confirmed by X-ray crystallography.

A general preparation for aromatic and aliphatic, cyclic as well as linear, symmetric and asymmetric difluoromethylenedioxy derivatives is described. The alcohols were reacted with thiophosgene to give thiocarbonates, which in turn were reacted with BrF3. The fluorination step is complete in seconds with moderate to high yields under mild conditions.

Both alkyl and aryl chlorothioformates could readily be obtained from the corresponding alcohols and thiophosgene. These families of compounds were treated with BrF3 to form the corresponding alkyl and aryl chlorodifluoromethyl ethers in 60–85 % yields. The method is suitable for constructing a variety of aliphatic as well as electron-deficient aromatic chlorodifluoromethyl ethers. The reactions proceed under mild conditions and short reaction times. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

A versatile and expeditious synthesis of taurine-derived thioureas, ureas, and guanidines using taurine isothiocyanate as the key intermediate is reported. Thioureas were obtained by a one-pot two-step procedure starting from taurine by the isothiocyanation reaction with thiophosgene in aqueous THF, followed by coupling with aliphatic and aromatic amines. Desulfurization of thiourea derivatives with yellow mercury(II) oxide gave access to either taurine-containing ureas or guanidines in a one-pot three-step fashion. This methodology was successfully applied to the preparation of a cyclodextrin-derived thiourea and guanidine with a taurine residue in their structures.

C 2 -Symmetrical chiral thioureas ( S , S )- 1 and ( S , S )- 2 were prepared in good yield by the reaction of 2 equiv of inexpensive ( S )-1-phenylethylamine, or the corresponding naphthyl analog, with 1 equiv of thiophosgene in the presence of excess triethylamine. The presence of asymmetric elements in ( S , S )- 1 and ( S , S )- 2 , and their capacity to act as receptors for anionic species via hydrogen bonding were exploited in the development of 1 H NMR spectroscopic enantiodiscrimination of chiral carboxylic acids. In particular, the diastereomeric complexes derived from thioureas ( S , S )- 1 and ( S , S )- 2 with ammonium salts of the chiral acids gave rise to well separated signals of the α-hydrogens and simple integration provides the corresponding enantiomeric ratios. Furthermore, it was observed that C α –H in the ( R ) enantiomers of the chiral α-hydroxy and α-amino carboxylic acids studied in this work consistently appears downfield relative to the same signals in the ( S ) enantiomers.

In this work we have performed a calculation on the rate constant of intersystem crossing T 1 → S 0 in thiophosgene, using a modified golden rule expression and a set of specific symmetrized vibrational coordinates for description of the potential energy surface (PES) and basis vibrational wavefunctions in both electronic states. The results from the present calculation were compared to those obtained previously using a different theoretical approach, as well as to experimentally measured data.

4 páginas, 2 tablas, esquemas., A practical synthesis of acylated glycosyl isothiocyanates from sugar oxazolines, by reaction with thiophosgene, is reported. In the absence of any additive, the reaction is governed by the reverse anomeric effect, leading to the equatorially oriented isothiocyanate. However, in the presence of copper(II) chloride, the reaction proceeds preferentially with retention of the configuration at the anomeric center, providing the axial anomer as the major product. Noteworthy, this strategy allows accessing per-O-acetylated glycopyranosyl isothiocyanates with 1,2-cis relative configuration (e.g., the alpha-anomer in the D-gluco and D-galacto series), a problem that was outside the scope of previous methodologies., We thank the Spanish Ministerio de Educación y Ciencia for financial support (contract nos. CTQ2006-15515-C02-01/BQU and CTQ2004-05854/BQU).

The vibrational spectrum and ground electronic state potential energy surface (PES) of thiophosgene (CSCl 2 ) have been studied quantum mechanically using a completely symmetrized Hamiltonian formalism and vibrational basis set, including all six molecular vibrational modes in the calculations. The calculated vibrational frequencies have been compared to the experimentally measured data by other authors. From a good fit achieved between the theoretical and experimental frequencies up to considerably high excess vibrational energies, the harmonic and some anharmonic (cubic and quartic) force constants of the molecular PES have been reliably determined.

Hydroxy-1-naphthaldehyde (1) was reacted with substituted anilines to aVord 1-(substituted phenyliminomethyl)naphthalen)-2- ols (2). The reduction of these imines by NaBH4 gave 1-((substituted phenylaminomethyl)naphthalen)-2-ols (3) which were cyclized with thiophosgene to give corresponding 2-substituted phenyl-1,2-dihydronaphto(1,2-e)oxazine-3-thiones (4). 3-p-Tolyl-3,4- dihydrobenzo(e)(1,3)oxazine-2-thione (8) was also obtained by the same way. The structures of these new compounds were determined by 1 H NMR, IR spectroscopic data and elemental analyses. AM1, PM3 and ab initio (at Hartree-Fock level with 3-21G basis set) methods were used to study the molecular geometry of the compounds. A complete infrared spectral analysis of the oxazines has been performed in this paper. Observed frequencies of the molecules were compared with calculated normal mode analysis which was car- ried out on the basis of RHF/3-21G method. Assignments of vibrational bands (in the range of 1760-400 cm i1 ) have been performed by taking into account the results of the ab initio vibrational analysis. The mechanism of the cyclization reaction between (3a) and thiophosgene was studied by the semi-empirical AM1 and ab initio (RHF) calculations. © 2006 Elsevier B.V. All rights reserved.

Over 400 X ∼ ← A ∼ transitions of SCCl2 have been measured by stimulated emission pumping from 209 to 240 THz above the X ∼ state zero point. The A ∼ state provides access to over 100 previously unassigned X ∼ state vibrational levels. The vibrational manifold of SCCl2 now has been mapped to maximum quanta in all six modes of (15, 4, 5, 18, 2, 2), providing a global view of vibrational dynamics. We report anharmonic constants that fit all currently available assigned vibrational energy levels. The onset of free energy flow has not been reached at E/h = 240 THz for states sampled here, in accordance with B ∼ state SEP data and a theoretical analysis.

Poly(pyridylureas) and poly(pyridylthioureas) were synthesized by reacting 2,6-diaminopyridine with phosgene and thiophosgene, respectively, using THF and pyridine as solvent. The synthesized polymers were characterized by IR-spectroscopy, elemental analysis, and X-ray photoelectron spectroscopy. Thermal stability of the polymers was determined by thermal degradation between 35°C and 700°C. The 50% weight loss of polypyridylureas was above 400°C while for the polypyridylthioureas it was above 450°C. Undoped poly(pyridylureas) and poly(pyridylthioureas) behave as semiconductors, σ = 10−9 (Ω cm)−1. After doping with I2 and SbF5, the electrical conductivity increases several orders of magnitude, σ = 10−7(Ω cm)−1. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007

WOS:000243672900006 Twenty one new thiophene-substituted 1,2,4-oxadiazo1-5(4H)-ones, 1,2,4-oxadiazol. 5(4H)-thiones, and 1,2,4-oxadiazin-5(6H)-ones were synthesized by the reaction of thiophene-ring substituted amidoximes with ethyl chloroformate, thiophosgene, and chloroacetylchloride, respectively. Their structure elucidation was performed by means of spectral measurements (IR, NMR, and MS) and physical data.

Thiophosgene (CSCl2), a chemical reagent used in numerous organic syntheses, exists in the monomeric form while its heavier silicon analogue [siliconthiodichloride (SiSCl2)] has been isolated so far as a dimer at room temperature and as a tetramer at 180 °C. Herein, we report on the first synthesis, isolation, and characterization of cyclic alkyl(amino) carbene (cAAC) stabilized siliconthiodichloride (cAAC)SiSCl2 (3) in the neutral monomeric form. 3 is synthesized via reaction of (cAAC˙)2Si2Cl4 (1) or (cAAC)2Si2Cl2 (2) with S8 in the temperature range of −78 to 20 °C. An NHC [NHC = N-heterocyclic carbene] analogue of 3 is not isolated when (NHC)SiCl2 is reacted with S8. The bright yellow colored compound 3 is soluble in polar organic solvents. It is stable at room temperature for a month under an inert atmosphere. 3 decomposes above 160 °C. The monomeric molecular structure of 3 has been unambiguously confirmed by X-ray single crystal diffraction. 3 is also characterized by NMR, UV-vis, and IR spectroscopy. The bonding and electron density distributions of 3 have been further studied by theoretical calculations.

A novel, high-yielding, one-step synthesis of 2-chloroquinazolin-4-ols and analogous bicycles from 2-aminoamides using thiophosgene is described. The scope of the reaction includes aminothioamides, amino acids, and fused heterocycle derivatives, furnishing quinazolines, oxazinones, and substituted fused pyrimidine bicycles, respectively. On the basis of observed results with substituted analogues, a mechanism for this transformation is thought to occur via an isothiocyanate intermediate followed by an unexpected chemoselective reaction of thiophosgene on the thiol intermediate.

2-Thioxo-1,3-oxazepine-4,7-dione compounds were obtained via triethylamine-catalyzed condensation of maleamic acids with thiophosgene under anhydrous conditions. This method features relatively a simple methodology, use of inexpensive reagents, convenient operating conditions and high yields.

6-Bromo-quinazolinone derivatives were prepared and evaluated for the ability to inhibit cyclooxygenase-2 (COX-2). An extensive structure–activity relationship work was carried out, thus some potent and selective COX-2 inhibitors were identified. The key compound isothiocyanate was prepared through a simple and ecological method using di-2-pyridyl thionocarbonate in substitution of the thiophosgene, a potential air pollutant. The cyclization reaction of intermediate derivatives was developed through the methods reporting by Wamhoff. The anti-inflammatory activity of the derivatives (5–12) was evaluated by determining (by Western blot) the expression of cyclooxygenase (COX)-2, of inducible NO synthase (iNOS) and of intercellular adhesion molecule-1 (ICAM-1). The biological assays showed that the derivatives 7, 9, 10, 12 act as potent inhibitors of COX-2, iNOS, and ICAM-1 expression in human keratinocytes NCTC-2544 cells. This work showed that the new derivatives could be used as a novel class of anti-inflammatory agents.

Nearly a 1000 X ∼ ← B ∼ transitions of jet-cooled SCCl2 have been measured by stimulated emission pumping. The observed rovibrational band contours cover the 210–330 THz region. A statistical autocorrelation analysis of the spectra answers a key question about the state space model of vibrational energy flow: is the dilution factor σ, which describes how many eigenstates participate in an optically ‘bright’ state due to anharmonic mixing, distributed according to a bimodal probability distribution P(σ) or not? Our SEP data supports a bimodal distribution predicted by state space models.

Poly(carbonates) and poly(thiocarbonates) containing silicon in the main chain and derived from the diphenols bis(4-hydroxyphenyl)-dimethylsilane, bis(4-hydroxyphenyl)-ethylmethylsilane, and bis(4-hydroxyphenyl)-diethylsilane with phosgene or thiophosgene, respectively, were synthesized under phase transfer conditions, using several phase transfer catalysts. Polymers were characterized by spectroscopic methods (IR and 1 H, 13 C, 29 Si NMR) and the results were evaluated by the yields and the η inh values. In general the effectiveness of the phase transfer process was low, the best results being obtained when the NaOH concentration was increased from the stoichiometric due to a salting-out effect. However, at higher concentrations hydrolytic process were observed. Poly(carbonates) and poly(thiocarbonates) showed, in general, the same trend with the catalysts.

5-Epithiohydantocidin, N -alkyl and N -glycosylthiohydantoin spironucleosides are prepared from glycosylaminoesters and from furanoid and pyranoid methyl isothiocyanatoulosonates. The aminoesters and the isothiocyanates are obtained, in a stereocontrolled manner, from sugar spiroacetals through a high-yielding sequence involving ring opening with trimethyl azide, formation of an ester group, reduction of the azide, and, in the case of isothiocyanates, reaction with thiophosgene.

Crosslinked hydrogels from 2-hydroxyethyl methacrylate (HEMA), ethylene dimethacrylate and polymerizable active esters based on N-methacryloylated ω-amino acids were prepared and modified with excess of ethane-1,2-diamine or hexane-1,6-diamine. 4-Isothiocyanatophenyl mannopyranoside or 6-(4-isothiocyanatobenzamido)hexyl mannopyranoside were used to bond d -mannose to hydrogel matrix through thioureylene groups.

The reaction of the α and β forms of C3S52− with thiophosgene yields two isomeric carbon sulfides α,α-C4S6 and α,β-C4S6, respectively. The crystal structures of both compounds could be determined for the first time. Both structures are made up of almost planar molecules. The α,α-isomer (1,3-dithiolo-(4,5-d)-1,3-dithol-2,5-dithione) is D2h-symmetric, while the α,β-isomer is approximately Cs-symmetric. In the molecules of both isomers the two different C3S5 units are retained without significant alterations of structural parameters. α,α-C4S6 is unstable with respect to α,β-C4S6. The molecular rearrangement can be induced by a short thermal treatment at 150 °C. Significant differences are found in the mass spectra fragmentation patterns. Only α,β-C4S6 shows an intense signal for C3S2+ and is therefore a potential source for the synthesis of carbon subsulfide via flash vacuum pyrolysis. Only α,β-C4S6 forms a stable adduct with I2. α,β-C4S6·I2 was already known (F. L. Lu, K. M. Keshavarz-K, G. Srdanov, R. H. Jacobson and F. Wudl, J. Org. Chem., 1989, 54, 2165, ), but a second polymorph is formed on crystallisation from a different solvent. The two polymorphic forms do not show differences in the structures of the individual molecules but show a different packing pattern. α,β-C4S6·I2 is remarkably thermally stable. Thermal analysis shows that I2 cleavage occurs in that temperature region above 200 °C when C–S bonds are broken and CS2 and I2 are simultaneously liberated. Performed at 270 °C thermolysis of α,β-C4S6·I2 yields under cleavage of I2 and CS2 a black polymeric carbon sulfide (CS)x which is probably a mixture of graphitic carbon and unidentified amorphous polymeric carbon sulfides.

A line-by-line rotational analysis of a selected group of bands in the high-resolution A ˜ 1 A 2 ( n π ∗ ) ← X ˜ 1 A 1 fluorescence excitation spectrum has been carried out to derive the structure of thiophosgene in the A 1 A 2 ( n π ∗ ) or S 1 electronic state. The fit of the rotational line structure yields changes of +0.094 A for the CS bond relative to the S 0 value of 1.600 and −0.007 A for the CCl bond (1.727 A). The ClCCl bond angle increases by +6.4° (111.2°) while the out-of-plane angle advances to 23.9°. The in-plane a - and b -principal axes are susceptible to axis-switching mediated by chlorine 35–37 isotope substitution and also by excitation to the A state. In the X ˜ or S 0 ground state, the a -axis lies along the CS bond for the 35 Cl 2 CS isotopomer and switches under chlorine isotope substitution in 37 Cl 2 CS to the in-plane perpendicular direction. Electronic excitation also induces a / b axis-switching giving rise to anomalous rotational line intensities in the centers of the 35 Cl 2 CS bands.

Two novel N-substituted-3beta-phenyltropane alkaloids have been labeled with iodine-125 for use as irreversible probes of dopamine transporter (DAT) binding sites. One contains an iodoaryl azide moiety for photolabeling, while the other bears an iodoaryl isothiocyanate for direct conjugation. Both radioligands were prepared in a one-flask procedure by electrophilic radioiodination of the corresponding aniline under no-carrier-added conditions, followed either by diazotization and treatment with sodium azide, or by addition of thiophosgene under basic conditions. Specifically, (-)-N-[4-(3-[(125)I]iodo-4-azidophenyl)butyl]-2beta-carbomethoxy-3beta-(4-chlorophenyl)tropane ([(125)I]MFZ-2-24) and (-)-N-[4-(3-[(125)I]iodo-4-isothiocyanophenyl)butyl]-2beta-carbomethoxy-3beta-(4-chlorophenyl)tropane ([(125)I]MFZ 3-37) were synthesized. Isolation by reversed-phase HPLC and solid-phase extraction gave good average yields of [(125)I]MFZ-2-24 (67%, n = 5) and [(125)I]MFZ-3-37 (45%, n = 3) with high radiochemical purities (96-99%) and specific radioactivities (2000 mCi/micromol). The utility of the radioligands was demonstrated by their covalent linkage to rat striatal membranes, and immunoprecipitation of a single radiolabeled band at 80 kDa corresponding to the full-length DAT.

Poly(carbonates) and poly(thiocarbonates), containing germanium in the main chain and derived from the diphenols bis(4‐hydroxyphenyl)‐dimethyl‐germane, bis(4‐hydroxyphenyl)‐diethyl‐germane, and bis(4‐hydroxyphenyl)‐dibutyl‐germane reaction with phosgene and thiophosgene, respectively. The products were synthesized under phase transfer conditions, using two phase transfer catalysts. The products were characterized by spectroscopic methods. The results were evaluated by the yields and ηinh values which showed different behaviors for poly(carbonates) and poly(thiocarbonates). The yields and the ηinh values for the poly(carbonates) were low due to a hydrolytic process when the NaOH concentration was increased. For the poly(thiocarbonates) the phase transfer was effective and also there was an increase of both parameters when the NaOH concentration was increased, due to a salting out effect.

Thiophosgene was used as a reagent for connecting different light and/or UV protecting fragments. Reaction of thiophosgene with stabilizers bearing a hydroxyl group leads to the corresponding chlorothiocarbonates. Their subsequent reactions with other stabilizers bearing a hydroxyl group lead to an unsymmetrical thioester bearing two different protecting fragments. 2,4-Dihydroxybenzophenone and 2,2,6,6-tetramethylpiperidine derivatives were chosen as hydroxyl partners of thiophosgene.

We present the results of experimental and theoretical studies of the speed-dependent spin–orbit state distributions of chlorine photofragments produced in the photodissociation of thiophosgene (CSCl 2 ) at 235 nm. Three-dimensional imaging has been employed for observing chlorine photofragments in their ground (Cl) and excited (Cl * ) spin–orbit states. The kinetic energy distributions for Cl and Cl * fragments reflect excitation of several electronic states of the partner fragment CSCl. The spin–orbit branching ratio of P (Cl * )/[ P (Cl) + P (Cl * )] was found to depend on the kinetic recoil energy increasing from 0.1 for low kinetic energy to 0.8 for high kinetic energy. The theoretical interpretation is based on the computation of the CSCl 2 potential energy surfaces (PES) along the C–Cl bond. Two completely different methods of determination of the PES were applied for small and for large values of the C–Cl bond separation R . In case of small and intermediate R values time-dependent density-functional theory has been used. In case of large R values we used an asymptotic method of computation of the PES, which is a generalisation of the Heitler–London approach for many-electron systems. Basis molecular wavefunctions with definite values of the total spin S and the spatial and spin reflection symmetry σ v with respect to reflection of the total electronic wavefunction in the molecular plane were used. The developed theoretical approach was used for the assignment of the molecular states involved in the photodissociation and for the qualitative explanation of the non-statistical population of the spin–orbit states of the chlorine photofragments as function of the kinetic energy. The spin–orbit branching ratio of P (Cl * )/[ P (Cl) + P (Cl * )] predicted by the theory strongly depends on the quantum state of the CSCl fragment. It is large in case of the CSCl(X) + Cl and CSCl(A) + Cl channels and small in case of the CSCl(B) + Cl channel which explains the experimental results.

One-photon excitation of the S0(X) thiophosgene to the S1(A) state, followed by photodepletion of the S1→S0 fluorescence by Sn (n=2,3)←S1 excitation, by another photon, reveals the presence of a dark S3(C) state in the vicinity of the B1A1(ππ*),S2, state. The measured polarization and the vibrational structure of the C←A absorption are consistent with the C state being the 1B2(nσ*) state, predicted by the CASSCF calculations of Strickler and Gruebele [Chem. Phys. Lett. 349 (2001) 137]. The dominant decay channel of the C1B2(nσ*) state is shown to be the direct internal conversion to the X1A1 state.

The collision-free S 1 [A 1 A 2 (nπ*)] thiophosgene, with small ( 9284 cm - 1 ) excess vibrational energies, does not exhibit radiationless transitions to bound electronic states (So and T 1 ), as evidenced by intense A → X fluorescence with nearly constant lifetimes. The lack of radiationless transitions can be traced to the absence of the promoting mode for the 1 A 2 → 1 A 1 internal conversion and the vanishingly small spin-orbit coupling and very small Franck-Condon factor for the 1 A 2 (nπ*) → 3 A 2 (nπ*) intersystem crossing. In the intermediate range of excess energies (3484-9284 cm - 1 ), fluorescence is not observed, consistent with the occurrence of predissociation. Quantum beat-modulated fluorescence decays, attributable to 1 A 2 (nπ*)- 3 A 1 (ππ*) perturbations, have been observed for excitation of 1 1 2 1 3 1 4 1 and nearby S 1 vibronic levels. This places the b 3 A 1 (ππ*) state at about 20 350 cm - 1 above the ground electronic state, in excellent agreement with the existing estimate. Interestingly, the S, radiative lifetime is about an order of magnitude shorter in a supersonic jet as compared to the vapor phase at room temperature, indicating that the probability of the vibronically induced A 1 A 2 (nπ*)-X 1 A 1 radiative transition is significantly reduced at higher temperatures, due probably to Coriolis coupling.

The vibrational structure of the B 1A1(ππ*) electronic state of jet cooled thiophosgene, Cl2CS, has been studied by laser induced fluorescence (LIF) excitation spectroscopy through the one-photon process B 1A1←X 1A1 and by optical–optical double resonance (OODR), spectroscopy. Two OODR schemes were used to probe the B 1A1 state. One uses selected vibronic levels of the singlet A 1A2(nπ*) state while the second scheme uses the companion triplet, a 3A2(nπ*) as the intermediate level. The one-photon LIF and the two-photon OODR schemes use different optical selection rules and the two sets of spectra contain very different information. The analyses of the vibrational structure confirmed the existing assignments for the Q1 (C=S stretch), Q2 (C–Cl stretch), and Q4 (out-of-plane) modes, and reversed the assignments for the Q3 (sym. Cl–C–Cl bend) and Q6 (antisym. Cl–C–Cl bend) modes. The barrier height to molecular inversion was revised upwards to 1495 cm−1 from an analysis of the (−)−(+) inversion splittings extracted from the ν4″=471 cm−1 “hot” band intervals in the “warm jet” one-photon LIF spectra. The regularity of the patterns of the Dixon–Western bands and the constant connecting wave-number intervals allowed these bands to be assigned to the activity of ν3″. The loss of fluorescence and the shortening of the lifetime at higher vibrational excitation energies is attributed to the crossing of the B 1A1(ππ*) and C 1B2(nσ*) electronic states at longer C=S bond distances.

The synthesis of the titled amino-ester 3 is described and its hydrolysis and chloroacetylation led to the acid 5 and acetamide 7 , which were cyclized to the pyrazolopyridones 6 and 8 , respectively. Condensation of 3 with 2,5-dimethoxytetrahydrofuran afforded the pyrrolylpyrazole 9 , which underwent cyclization by action of PPA to give pyrazolopyrrolizine 10 . Treating 3 with thiophosgene gave the pyrazolyl isothiocyanate 11 , which added aniline to yield the thiourea derivative 12 , and cyclized to give pyrazolopyrimidinethiones 13-15 . Condensation of 3 with formamide furnished pyrazolopyrimidine 16 , while with triethyl orthoformate produced the ethoxymethyleneaminopyrazole 18 , which condensed with hydrazine to give the aminopyrazoloprimidine 19 . Reaction of 3 with Lawesson's reagent resulted in the pyrazolothiazaphosphinine 21 . Also the cyclization reaction of the compound 3 with malononitrile and its mixtures with carbon disulfide, phenyl isothiocyanate, or benzaldehyde led to the formation of a...

The reaction of thiophosgene with 2,2,6,6-tetramethylpiperidine-1-oxyl (used as a model nitroxyl radical) was examined. 2,2,6,6-Tetramethylpiperidine and 2,2,6,6-tetramethyl-1-hydroxypiperidine were identified as products. The reaction is not competitive with the reaction of thiophosgene with an amino group. Thus, three nitroxides with an isothiocyanate group were synthesized from thiophosgene and the nitroxides containing the amino substituent.

Coupling of biotin with CpFe(CO) 2 (η 1 - N (1)-4-aminosulfonamido) ( 1a ) and CpFe(CO)(P(OMe) 3 ) (η 1 - N (1)-4-aminosulfonamide) ( 1b ) afforded corresponding metallo-carbonyl biotin amides 2a – b . Reaction of N e -biotinyl- l -lysine (biocytin) with CpFe(CO) 2 (η 1 - N -3-isothiocyanatophtalimidato) ( 4a ), CpFe(CO) 2 (η 1 - N -4-isothiocyanatophtalimidato) ( 4b ), CpFe(CO) 2 (η 1 - N (1)-4-isothiocyanatosulfonamido) ( 5 , this compound was prepared from 1a and thiophosgene and its structure confirmed by spectral data and by the X-ray diffraction method) gave bioconjugates 6a – c . The HABA-avidin test revealed high affinities of all synthesised bioconjugates to avidin.

The thermal properties of poly(carbonates) and poly(thiocarbonates) containing silicon or germanium in the main chan, derived from thediphenolsbis(4-hydroxy-phenyl)-dimethylsilane, bis(4-hydroxyphenyl)-dimethylgermane, bis(4-hydroxy-phenyl)-diphenylsilane and bis(4-hydroxyphenyl)-diphenylgermane, and phosgene or thiophosgene, were studied by differential scanning calorimetry and dynamic thermogravimetry. Polymers containing phenyl groups bonded to the heteroatoms showed higher Tg values, and the same was valid for those with Ge in respect to Si. Poly(carbonates) showed higher Tg values than poly(thiocarbonates). The thermogravimetric curves revealed that poly(carbonates) are more stable than poly(thiocarbonates)and the same is valid for those containing Ge with respect to the silicon-containing polymers. The kinetic parameters associated with the degradation process, showed that probably there are complex degradation mechanisms, which depend on the heteroatom in the main chain, Si or Ge, and the groups bo...

Isothiocyanates have gained considerable attention for their role as potent chemopreventive agents. Sulforaphane, 1a (SFN), a naturally occurring isothiocyanate, was isotopically labelled in five steps starting from 3-(methylthio)-1-propanol (2). Reacting 2 with tosyl chloride in the presence of Et3N yielded the tosylate 3. Gently refluxing 3 with K14CN in DMF gave the nitrile 4b. Reduction to the amine 5b was achieved using BH3-THF. Oxidation with 30% hydrogen peroxide followed by treatment with thiophosgene yielded (±)[1-14C]SFN, 1b. The overall radiochemical yield was 4.4% based on the starting K14CN. Copyright © 2003 John Wiley & Sons, Ltd.

In this study, a protocol for the synthesis of symmetrical diaryl trithiocarbonates through the one-pot copper-catalyzed coupling reaction of sodium sulfide, carbon disulfide, and aryl compounds in DMF solution is presented. This method allows the synthesis of symmetrical diaryl trithiocarbonates without the use of highly toxic thiophosgene, and also, commercially available aryl halides were used instead of less available, toxic thiols.