19807-41-1

Upstream product

• 1269766-24-6 C₇H₅Cl*C₉H₁₂O₃ 
• 19016-92-3 phenylchlorodiazomethane 
• 103-71-9 phenyl isocyanate 
• 4460-46-2 3-chloro-3-phenyl-3H-diazirine 

Downstream Products

• 1125-88-8 benzaldehyde dimethyl acetal 
• 35364-99-9 ((S)-Chloro-methoxy-methyl)-benzene 
• 31614-79-6 (chloro(phenyl)methyl)triethylsilane 
• 24344-83-0 Succinimidyl-Radikal 
• 3170-67-0 dichloro-phenyl-methyl 
• 94-49-5 1,2-ethanediol, dibenzoate 
• 3418-37-9 2-phenyl-2-phenylchloromethyl-1,3-dioxolane 
• 91766-86-8 1-chloro-1-phenyl-2,2,3-trimethylcyclopropane 
• 13153-95-2 ((1R,3S)-1-Chloro-2,2,3-trimethyl-cyclopropyl)-benzene 
• 13153-95-2 ((1R,3R)-1-Chloro-2,2,3-trimethyl-cyclopropyl)-benzene 
• 3141-40-0 1-chloro-1-phenyl-2,2,3,3-tetramethylcyclopropane 
• 132249-18-4 Phenyl(2,4,6-tri-t-butylphenyl)acetylene 
• 68003-55-4 benzylidene allylamine 
• 3335-22-6 thiobenzoyl chloride 

Relevant academic research and scientific papers

A carbene-carbene complex equilibrium

Phenylchlorocarbene, generated by laser flash photolysis of phenylchlorodiazirine, formed highly stable φ-type complexes with 1,3,5-trimethoxybenzene in pentane. The carbene and carbene complexes were in equilibrium. We measured the equilibrium constant (

Imidazo[1,5-a]pyridinium salts from phenylchlorocarbene and 2-pyridyl Schiff bases: Synthesis, reaction mechanism and effect of rotamerism

3-Phenylimidazo[1,5-a]pyridinium salts are easily prepared in excellent yield by thermolysis of phenylchlorodiazirine in the presence of 2-pyridyl Schiff bases (2-Pyr-CH=NR, where R is an aromatic or alkyl group). When the reaction is conducted in an alkane solvent, the salts precipitate and are easily obtained with a high level of purity after filtration and repeated washing of the precipitate with a nonpolar solvent. A laser-flash photolysis study of the reaction mechanism reveals that the phenylchlorocarbene produced by decomposition of the diazirine reacts with the Schiff base to give two different ylides. The intramolecular cyclization of these two ylides yields the same intermediate product, which rapidly eliminates a chlorine anion. Neither semi-empirical calculations of the energy barriers for the formation and cyclization of the various possible ylides, nor comparison of their calculated and experimental absorption spectra, allow us to determine whether the two ylides are rotamers of a pyridinium ylide or a pyridinium ylide and an iminium ylide. Only the comparison of systems where R is a cyclohexyl or a tert-butyl group indicates that the two ylides are rotamers of a pyridinium ylide. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

The thermodynamics of the formation of pyridinium ylides from carbienes

The enthalphies of reaction for complexion of methyl- and phenylchlorocarbene with substituted pyridines are determined by photoacoustic calorimetry. The enthalpies are similar for the two carbenes and can be related to the pKa's of the pyridin

Femtosecond dynamics of isolated phenylcarbenes

Understanding the primary photophysical processes in molecules is essential for interpreting their photochemistry, because molecules rarely react from the initially excited electronic state. In this study the ultrafast excited-state dynamics of chlorophenylcarbene (CPC) and trifluoromethylphenylcarbene (TFPC), two species that are considered as models for carbene dynamics, were investigated by femtosecond time-resolved pump probe spectroscopy in the gas phase. Their dynamics was followed in real time by time-resolved photoionization and photoelectron imaging. CPC was excited at 265 nm into the 3 1A′ state, corresponding to excitation from a π-orbital of the aromatic ring into the LUMO. The LUMO contains a contribution of the p-orbital at the carbene center. Three time constants are apparent in the photoelectron images: A fast decay process with τ1 ≈ 40 fs, a second time constant of τ2 ≈ 350 fs, and an additional time constant of τ3 τ 1 ps. The third time constant is only visible in the time-dependence of low kinetic energy electrons. Due to the dense manifold of excited states between 3.9 and 5 eV, known from ab initio calculations, the recorded time-resolved electron images show broad and unstructured bands. A clear population transfer between the states thus can not directly be observed. The fast deactivation process is linked to either a population transfer between the strongly coupled excited states between 3.9 and 5.0 eV or the movement of the produced wave packet out of the Franck-Condon region. Since the third long time constant is only visible for photoelectrons at low kinetic energy, evidence is given that this time constant corresponds to the lifetime of the lowest excited A 1A′ state. The remaining time constant reflects a deactivation of the manifold of states in the range 3.9-5.0 eV down to the A 1A′ state. Copyright

Singlet Halophenylcarbenes as Strong Hydrogen-Bond Acceptors

Chlorophenylcarbene and fluorophenylcarbene were generated in water-doped argon matrices at cryogenic temperatures by photolysis of the corresponding matrix-isolated diazirines. When diffusion of H2O in solid argon was induced by annealing of the matrices at temperatures above 20 K, hydrogen-bonded complexes between the carbenes and water were formed. UV photolysis of these complexes resulted in the formation of benzaldehyde and hydrogen halides HX. The same products were obtained after photolysis of the diazirines in amorphous water ice. Obviously, the primary insertion product of the carbenes into H-OH is unstable under these conditions, and benzaldehyde is formed via secondary photolysis. The stable primary photochemical insertion product of chlorophenylcarbene into an O-H bond was observed in the reaction of the carbene with methanol.

Hammett analysis of a family of carbene-carbene complex equilibria

p-X-substituted phenylchlorocarbenes (X = NO2, CF3, Cl, H, Me, and MeO) form π-type complexes with trimethoxybenzene in pentane. The carbenes and complexes are in equilibrium, and logarithms of the measured equilibrium constants are well correlated by Hammett σp constants with ρ = 2.48. The carbene complexes are characterized by UV-vis spectroscopy, and computational analysis is afforded by DFT calculations.(Figure Presented)

Direct observation of carbene and diazo formation from aryldiazirines by ultrafast infrared spectroscopy

Ultrafast laser flash photolysis (λex = 270 nm) of phenyldiazirine produces transient infrared absorptions at 2040 and 1582 cm-1. The first band is assigned to phenyldiazomethane, and the second is assigned to singlet phenylcarbene. This assignment is consistent with DFT calculations. Diazo band integration reveals that photoisomerization from diazirine to diazo occurs within a few picoseconds of the laser pulse. The majority of carbene produced is also formed instantaneously. Copyright

Hammett studies of aryldichloromethide carbanion reactions

Rate constants were measured for the capture of para-substituted phenylchlorocarbenes by chloride ions to form aryldichloromethide carbanions and for the additions of these carbanions to acrylonitrile. Hammett analyses give ρ = +0.86 for the former reacti

First direct observation of reactive carbenes in the cavities of cation-exchanged Y zeolites

(Equation presented) Herein we report the first direct observation of reactive carbenes within the cavities of cation-exchanged Y zeolites. Chloro(phenyl)- and bromo(phenyl)carbenes were generated upon laser photolysis of 3-halo-3-phenyldiazirines incorporated within dry zeolites and the absolute reactivity of the carbenes was investigated as a function of counterbalancing cation and coincorporated quenchers in order to elucidate the behavior of these intermediates within zeolites. Product analysis performed upon thermolysis of the diazirine in Y zeolites yielded products that were identified as those derived from the carbene.

Time-resolved IR studies of & α-lactones

A series of & α-lactones were generated from the reaction of phenylchlorocarbene, 4-nitrophenylchlorocarbene, diphenylcarbene, bis(4-nitrophenyl)carbene and bis(4-methoxyphenyl)carbene with carbon dioxide and examined by nanosecond time-resolved infrared (TRIR) spectroscopy. Estimated second-order rate constants for the reaction of these carbenes with carbon dioxide indicate that more nucleophilic carbenes react at faster rates, in agreement with previous low-temperature matrix experiments. Spectral TRIR data confirms that the structure of & αlactones is dependent both on substituents at the & α-carbon and on solvent polarity, with electron-donating substituents and polar solvents favoring a zwitterionic ring-opened structure as opposed to the three-membered ring oxiranone form. B3LYP calculations using self-consistent reaction field (SCRF) methods also provide support for these experimental investigations. Copyright