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Thiophosgene is one of the principal C=S building blocks in synthetic chemistry. At room temperature, thiophosgene is a red liquid. While its properties in the liquid and gaseous states are well known, a comprehensive characterization of thiophosgene in its solid state is presented here. Differential scanning calorimetry shows that thiophosgene forms a supercooled melt before rapidly crystallizing. Its melting point is 231.85 K (−41.3 °C). At 80 K, thiophosgene crystallizes in space group P63/m [No. 174, a = b = 5.9645 (2), c = 6.2835 (3) Å, V = 193.59 (2) Å3]. The molecule shows a distinct rotational disorder: all S and Cl positions are of mixed occupancy and the disorder does not resolve at temperatures as low as 10 K, as was shown by neutron powder diffraction. Infrared, Raman and inelastic neutron scattering spectra were collected and assigned with the aid of quantum chemical calculations. A larger ordered structural model allowed for better agreement between the measured and calculated spectra, further indicating that disorder is an inherent feature of solid‐state thiophosgene. [ABSTRACT FROM AUTHOR]

The theoretical examination of the interaction among formaldehyde, phosgene, and thiophosgene molecules on both pristine Zn12O12 nanocage and TM-decorated (Cu, Ni, Ti, and Cr) Zn12O12 nanocage is conducted using density functional theory (DFT). The Zn12O12 nanocage by doping of Cu, Ni, Ti, and Cr atoms remarks in altering the electronic properties and actively reassuring the adsorption of these toxic gases. The finding revealed that Zn12O12 nanocages doped with metal atoms enhance reactivity. In this study, the adsorption energy, dipole moment, charges from natural bond orbitals (NBO), global reactivity parameters, and frontier molecular orbitals (FMOs) were analyzed. The results show that phosgene and thiophosgene are physisorbed on Zn12O12 nanocage with adsorption energies of -10.63, and -9.41 kcal/mol, respectively. The decoration of Zn12O12 nanocage with transition metals (Cu, Ni, Ti, and Cr), efficiently enhanced the adsorption of H2CO, COCl2, and CSCl2. The adsorption of these harmful gases on TM-decorated Zn12O12 nanocage resulted in strong chemisorption. Among the selected warfare agents, CSCl2@Cr-Zn12O12 and H2CO@Ti-Zn12O12 show the highest value of adsorption energy (− 77.86 and − 75.37 kcal/mol, respectively). These complexes also exhibit high chemical hardness value and low softness value suggesting their higher stability and lower reactivity as compared to other complexes. Moreover, the results of recovery time suggested that COCl2 can be desorbed from Ni-Zn12O12 with a recovery time of 0.014 s. Therefore, it is suggested that the Ni-Zn12O12 nanocage may be used as a potential reusable sensor for the detection of phosgene at room temperature due to its high sensitivity and short recovery time. Additionally, the results suggested that the adsorption energy and electrical conductivity of toxic gases on decorated Zn12O12 nanocage increase, potentially improving sensitivity towards these toxic gases. [ABSTRACT FROM AUTHOR]

The density functional B3LYP is used to investigate the effect of decorating the silver (Ag) atom on the sensing capability of an AlN nanotube (AlN-NT) in detecting thiophosgene (TP). There is a weak interaction between the pristine AlN-NT and TP with the sensing response (SR) of approximately 9.4. Decoration of the Ag atom into the structure of AlN-NT causes the adsorption energy of TP to decrease from − 6.2 to − 22.5 kcal/mol. Also, the corresponding SR increases significantly to 100.5. Moreover, the recovery time when TP is desorbed from the surface of the Ag-decorated AlN-NT (Ag@AlN-NT) is short, i.e., 24.9 s. The results show that Ag@AlN-NT can selectively detect TP among other gases, such as N2, O2, CO2, CO, and H2O. [ABSTRACT FROM AUTHOR]

• The sensing capability of novel C 24 N 24 nanocage towards chemical warfare agent's (CWAs) phosgene (COCl 2) and thiophosgene (CSCl 2) is explored. • The NBO, QTAIM, NCI, MEP, and DOS analyses are performed employing DFT. • Excellent sensitivity (∼0.050), recovery time (∼3 × 10−14s−1), and electrical conductivity (∼1.84 × 109) are observed. • Results ascertain the elevated reactivity and an imperishable sensitivity of the C 24 N 24 nanocluster toward investigated CWAs. • C 24 N 24 nanocluster is recommended as a promising influential sensor for phosgene and thiophosgene detection. Chemical warfare agents (CWAs) are highly poisonous and dangerous to all forms of life. Their rapid discovery and removal are crucial for the protection of people and the environment. Current technology still falls short of the 100 % efficiency threshold. Therefore, we make use of the efficient three-dimensional C 24 N 24 -nanostructured material for the rapid detection and electrochemical sensing of CWAs phosgene (COCl 2) and thiophosgene (CSCl 2) by employing benchmark DFT and TD-DFT investigations. Nine stable configurations of C 24 N 24 nanocluster were quantum chemically designed facing through chlorine, oxygen, sulphur atoms of phosgene and thiophosgene and with their planar orientations on the large and small cavities of the nanocluster. Optimization of geometry, FMO, adsorption energies, NBO, QTAIM, and NCI, were the methods for evaluating the interaction between chemical warfare agents and the nanocluster. Fine-tuning of electronic properties; recovery time (∼3 × 10−14s−1), electrical conductivity (∼1.84 × 109), sensitivity (∼0.050), electrophilicity index (1.76–1.68 eV), hardness (3.52–3.37 eV), softness (∼0.15 eV), energy gap (2.85–2.55 eV), and interaction distance (4.274±1.245A0), values ascertain the elevated reactivity and an imperishable sensitivity of the C 24 N 24 nanocluster towards the investigated CWAs. The energy gap, QTAIM, NCI, sensitivity, and recovery time analysis confirmed that the Pl*@C 24 N 24 -SC nanostructured material developed as the most suited surface for the effective finding of phosgene and Pl@C 24 N 24 -LC for thiophosgene. Adsorption energies of −8.490 and -8.507 kcal/mol for the Pl*@C 24 N 24 -SC and Pl@C 24 N 24 -LC complexes, respectively, were the deciding factors. The C 24 N 24 nanocluster has the highest sensitivity and shortest recovery time for S@C 24 N 24 -LC and Pl@C 24 N 24 -LC complex with the value of 0.0509 and 3.23 × 10−14s−1 which shows the potential of C 24 N 24 nanocluster as a promising influential sensing material to monitor CWAs phosgene and thiophosgene. This theoretical framework will assist experimentalists in detecting toxic CWAs by using C 24 N 24 nanocluster-based sensor. [Display omitted] [ABSTRACT FROM AUTHOR]

The present research surveyed thiophosgene gas adsorption on Co@B cluster utilizing MPW1PW91 functional. Seven feasible isomers of interaction between Co@B cluster and thiophosgene were regarded. The interaction, adsorption and cohesive energy values are measured in these molecules. The interactions between cluster and thiophosgene were investigated through energy decomposition analysis (EDA). Charge transfer between fragments were shown by electrophilicity-based charge transfer (ECT). Thermodynamics parameters of interaction between nano-cluster and thiophosgene gas were computed. QTAIM computations were applied to describe interaction between thiophosgene and Co@B . [ABSTRACT FROM AUTHOR]

The pyrimidine ring is a skeleton of particular interest that it is present in many compounds exhibiting biological and pharmaceutical activity. In the present work, some new pyrimidine derivatives were prepared via the formation of 5-oxo-4H-benzopyran (3), and its transformation to pyrimidine derivative (5) by reaction with benzamidine HCl. Compound 5 was subjected to react with thiophosgene to give isothiocyanate derivative 6. Phenacyl amine 7 was prepared by reaction of phenacyl bromide with hexamethylenetetramine under Delepine reaction condition. The reaction of compounds 6 and 7 in ethanol and drops of TEA afforded the imidazopyrmidinopyrimidine 8. Compound 8 was subjected to react with excess of POCl3 to give its corresponding 5-chloro-2,8-diphenyl-10-(ptolyl) imidazo[1,2-c]pyrimido[5,4-e]pyrimidine (9). Then compound 9 was reacted with different amines to give N- (aryl)-2,8-diphenyl-10-(p-tolyl)imidazo[1,2-c]pyrimido [5,4-e]pyrimidin-5-amine (10 a-k). The new imidazopyrimidinopyrimidine derivatives, 10a-k, were first assessed for their anti-tumor properties towards two cancer cell lines, namely human hepatic malignancy (HepG2) and breast (MCF-7) by utilizing an MTT assay at a sole strength of 10 µM. Compounds 10d, 10e, 10f, 10h, and 10i displayed very strong activity, which contains in general, electron-withdrawing groups. [ABSTRACT FROM AUTHOR]

Naturally occurring isothiocyanates are limited in number. These have been found to be present in some species of Cruciferae as progenitors, called glucosinolates, and are released from the injured plant by the enzyme myrosinase. On the other hand, there is a large number of synthetic isothiocyanates which constitute an important class of compounds. It is apparent that the chemistry of isothiocyanates has burgeoned over the years, and it continues to be a blossoming field. The attraction of isothiocyanates as synthons is obviously due to their diverse reactions and also due to their easy availability. It would not be out of place to record that, in comparison to isocyanates, their sulfur analogues, isothiocyanates, are less unpleasant and to some extent less hazardous to work with. In one of our investigations during 1984, we had to abandon the use of isocyanates as cyclocondensing agents because of the reluctance of a research scholar who was in the grip of a fear complex caused by the tragic death and crippling of a large number of Bhopal citizens due to the devastating accident in a chemical plant using methyl isocyanate. Since then we became interested in isothiocyanates. The purpose of this review is to present highlights of the various synthetic schemes to obtain the various kind of isothiocyanates. [ABSTRACT FROM AUTHOR]

Abstract: While thiophosgene finds widespread usage on a multi‐ton scale, its fluorinated counterpart S=CF2 is essentially unexplored in synthesis. Using experimental reactivity tests, ReactIR and computational techniques, we herein showcase that the solid (Me4N)SCF3 functions as a safe reservoir for S=CF2. A key feature is that the reactive electrophile is not simply released over time, but instead is liberated under activation with a protic nucleophile. The reactivity of S=CF2 is mild, allowing large‐scale and late‐stage synthetic applications without special reaction control. The mechanism was fully elucidated, including a rationalization of the role of the Me4N cation and the origins of selectivity. [ABSTRACT FROM AUTHOR]

In this work, using our vibrational variational calculation method and a recently derived refined quartic potential energy surface for S 0 thiophosgene, we have carried out large scale vibrational calculations to analyze the vibrational structure of this electronic state in the whole range of vibrational excitation energies down from the origin and up to the dissociation limit (at ↼20,000 cm ↙1 ). In the lower excited vibrational range we have achieved satisfactory coincidence of calculated to experimentally measured frequencies, while at the higher vibrational excitations our main objective has been to estimate what part of the available vibrational level density is effectively involved into the vibrational mixing and IVR. The results from our calculations have been compared to the available experimentally obtained dataset (obtained from synchrotron IR, SEP and LIF spectra) as well as to conclusions from the analyses by other authors using local coupling models. [ABSTRACT FROM AUTHOR]

In this work, using a recently derived refined potential energy surface for thiophosgene, we perform large scale vibrational calculations to explore the IVR characteristics and vibrational mixing at very high vibrational excitation energies, ranging up to the dissociation limit (at 20,000cm). The results from our calculations have been compared to the conclusions based on the available experimentally measured dataset (obtained from SEP and LIF spectra) as well as to the conclusions from the analyses by other authors using local coupling models. [ABSTRACT FROM AUTHOR]

Thiophosgene (Cl 2 CS) is a favorite model system for studies of photophysics, vibrational dynamics, and intersystem interactions. But its infrared spectra tend to be very congested due to hot bands and multiple isotopic species. This paper reports the first detailed study of the ν 1 (∼1139 cm − 1 ) and ν 5 (∼820 cm −1 ) fundamental bands for the two most abundant isotopologues, 35 Cl 2 CS and 35 Cl 37 ClCS, based on spectra with a resolution of about 0.001 cm −1 obtained at the Canadian Light Source far-infrared beamline using synchrotron radiation and a Bruker IFS125 Fourier transform spectrometer. The 2 ν 4 (∼942 cm − 1 ) and ν 2 + 2 ν 6 (∼1104 cm −1 ) bands are also studied here, but the ν 2 + ν 6 band (∼795 cm − 1 ) resisted full analysis. [ABSTRACT FROM AUTHOR]

In this work we present a full 6D quartic potential energy surface (PES) for S 0 thiophosgene in curvilinear symmetrized bond-angle coordinates. The PES was refined starting from an ab initio field derived from acc-pVTZ basis set with CCSD(T) corrections for electron correlation. In the present calculations we used our variational method that was recently tested on formaldehyde and some of its isotopomers, along with additional improvements. The lower experimentally known vibrational levels for 35 Cl 2 CS were reproduced quite well in the calculations, which can be regarded as a test for the feasibility of the obtained quartic PES. [ABSTRACT FROM AUTHOR]

Abstract: The synthesis of 2,2,4,4-tetrathio substituted 1,3-dithietanes and their intermediates by reaction of thiophosgene with carbonotrithioates or O-ethyldithiocarbonate is reported. Their reactivity against thermolysis and aminolysis was investigated. [Copyright &y& Elsevier]

The efficient synthesis of 4-substituted 5-thioxo-1,2,4-triazolidin-3-one derivatives (4-substituted thiourazoles) via domino combination of thiophosgene, aliphatic or aromatic amines, and ethyl carbazate is presented. [ABSTRACT FROM AUTHOR]

In this work an analysis of the highly vibrationally excited states of thiophosgene (SCCl) is made in order to gain insights into some of the experimental observations and spectral features. The states analysed here lie in a spectrally complex region where strong mode mixings are expected due to the overlap of several strong anharmonic Fermi resonances. Two recent techniques, a semiclassical angle space representation of the eigenstates and the parametric variation of the eigenvalues (level-velocities) are used to identify eigenstate sequences exhibiting common localization characteristics. Preliminary results on the influence of highly excited out-of-plane bending modes on the nature of the eigenstates suggest a possible bifurcation in the system. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

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 T and S 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 T/S 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, ClCS. 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 [ABSTRACT FROM AUTHOR]

A framework has been evolving for evaluation of mode of action (MOA) of rodent toxicity and carcinogenicity findings and their relevance to humans. Folpet produces duodenal glandular tumors in mice, but is not carcinogenic in rats. A wealth of information is available regarding folpet’s mode of action, providing an excellent example of how this tumor can be evaluated using this framework. Folpet reacts with thiol groups, and is rapidly hydrolyzed at pH 7. Both reactions produce thiophosgene that reacts with thiols and other functional groups. Folpet is not genotoxic in vivo. At sufficiently high, prolonged dietary doses, folpet irritates the mouse duodenum, resulting in cytotoxicity with consequent regenerative proliferation and ultimately tumor development. Forestomach lesions secondary to cytotoxicity are also induced. Dogs have stomachs similar to humans and show no evidence of gastrointestinal toxicity or tumor formation at exposure levels at least as high as rodents. The data support a MOA in mice involving cytotoxicity and regenerative proliferation. Based on MOA analysis and assessment of human relevance, folpet, like captan, another trichloromethylthio-related fungicide with similar toxic and carcinogenic effects, is not likely to be a human carcinogen at dose levels that do not cause cytotoxicity and regenerative proliferation. [ABSTRACT FROM AUTHOR]

Abstract: 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 ν 2 (∼504cm−1) and ν 4 (∼471cm−1) fundamental bands for the two most abundant isotopomers, 35Cl2CS and 35Cl37ClCS, based on spectra with observed line widths of ∼0.0008cm−1 obtained at the Canadian Light Source far-infrared beamline using synchrotron radiation and a Bruker IFS125 Fourier transform spectrometer. [Copyright &y& Elsevier]

Abstract: 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. [Copyright &y& Elsevier]

Abstract: 2-Hydroxy-1-naphthaldehyde (1) was reacted with substituted anilines to afford 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 1H 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 carried out on the basis of RHF/3-21G method. Assignments of vibrational bands (in the range of 1760–400cm−1) 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. [Copyright &y& Elsevier]

Abstract: 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. [Copyright &y& Elsevier]

Abstract: A line-by-line rotational analysis of a selected group of bands in the high-resolution fluorescence excitation spectrum has been carried out to derive the structure of thiophosgene in the à 1 A 2(nπ∗) or S 1 electronic state. The fit of the rotational line structure yields changes of +0.094Å for the CS bond relative to the S 0 value of 1.600 and −0.007Å for the CCl bond (1.727Å). 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 à state. In the or S 0 ground state, the a-axis lies along the CS bond for the 35Cl2CS isotopomer and switches under chlorine isotope substitution in 37Cl2CS 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 35Cl2CS bands. [Copyright &y& Elsevier]

Abstract: 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. [Copyright &y& Elsevier]

Practical, facile and high-yielding one-pot syntheses of different O-unprotected glycopyranosyl thioureas and thioureido bolaamphiphiles (two-step synthesis) and of 2-amino-4,5-dihydro-(1,2-dideoxy-β-d-glucopyranoso)[1,2-d]oxazoles (three-step synthesis) from glycopyranosylamines are reported. The method involves the preparation of O-unprotected β-d-gluco (and d-galacto)pyranosyl isothiocyanates which are in equilibrium with the corresponding 1,2-cyclic thiocarbamates, coupling with amines to afford glycosyl thioureas and treatment with yellow mercury (II) oxide to give trans-fused bicyclic isoureas. A d-gluco trehazolin analogue is prepared in this way. In situ transformation of N,N-dialkyl, N′-glucopyranosyl thioureas into the corresponding ureas is also reported. [Copyright &y& Elsevier]

In a previous report, we examined the possibility of ‘freezing’ intramolecular vibrational energy redistribution (IVR) in organic molecules by using optimal coherent control. Here we describe the new methodology developed to achieve stabilization of initially excited nonstationary states. Our approach combines an approximate but full-dimensional molecular vibrational Hamiltonian, a frequency-domain wavelet representation of the electric field, a fast symplectic propagator to compute the IVR decay, and simulated annealing optimization of the electric field parameters. We find that the complexity of the vibrational wavepacket increases sufficiently slowly with time, so that with available pulse shapers, vibrational dephasing can be ‘frozen’ for 1–2 orders of magnitude in time beyond the usual IVR decay time. Slowing the IVR clock into the multi-picosecond regime may allow the natural selective reactivity (via Franck–Condon factors) of the initially excited nonstationary vibrational states to emerge. [Copyright &y& Elsevier]

Three new diisothiocyanato-functionalized 2,2'-bipyridines have been synthesized in four consecutive steps. Starting from 4-amino-2-chloro- and 2-amino-6-bromopyridine, respectively, we first prepared the corresponding diamino-2,2'-bipyridines via homo- or Negishi cross-coupling reactions which were subsequently reacted with thiophosgene. [ABSTRACT FROM AUTHOR]

Although, the sensor applications of straight chain conducting polymers are well explored, but, the cyclic analogues are not much explored in this regard. The density functional theory calculations are performed to study the interaction behaviour of tetracyclic oligomers such as tetrapyrrole (4CP), tetrafuran (4CF) and tetrathiophene (4CT) for the detection of harmful gases like, phosgene, thiophosgene and formaldehyde. The most stable interaction configurations, interaction energies (E int), interaction distance (D int), SAPT0 energies, NCI, NBO charge transfer, HOMO-LUMO gaps and maximum absorbance are evaluated to understand the sensitivity and selectivity of these cyclic analogues toward poisonous gases. The results of all these properties illustrate that 4CP exhibits the highest sensitivity towards analytes with the sequence of formaldehyde > phosgene > thiophosgene. The interaction energies are −10.91, −9.03 and −7.58 kcal mol−1 for fd@4CP, ph@4CP and tph@4CP complexes, respectively. SAPT0 results depict that the electrostatic forces have strong influence in these complexes which indicate the presence of strong hydrogen bond between 4CP and analytes. However, this is not the case in other oligomer-analyte complexes especially in 4CT based complexes. The highest sensitivity of 4CP enables it to act as promising sensing material for formaldehyde, phosgene and thiophosgene as compared to 4CF and 4CT. Image 1 • Sensing affinities tetracyclic analogues have been investigated. • Toxic chemicals namely phosgene, thiophosgene and formaldehyde are investigated. • ωB97XD/6-31 + G (d, p) method of DFT has implemented. • Tetracyclic pyrrole has high sensitivity over furan and thiophene analogues. [ABSTRACT FROM AUTHOR]