19016-92-3

Upstream product

• 4460-46-2 3-chloro-3-phenyl-3H-diazirine 
• 1670-14-0 benzamidine monohydrochloride 

Downstream Products

• 5082-83-7 C₁₅H₁₃Cl 
• 5082-83-7 C₁₅H₁₃Cl 
• 83320-84-7 9-Chlor-exo-9-phenylbicyclo<6.1.0>nona-2,4,6-trien 
• 83320-84-7 exo-9-Chlor-endo-9-phenylbicyclo<6.1.0>nona-2,4,6-trien 
• 19807-41-1 chlorophenylcarbene 
• 20420-98-8 (CH₃CH₂CH₂CH₂)3SnCHClC₆H₅ 
• 83320-85-8 C₃₅H₂₆O 

Relevant academic research and scientific papers

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

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.

1,2,4,6-CYCLOHEPTATETRAENE: THE KEY INTERMEDIATE IN ARYLCARBENE INTERCONVERSIONS AND RELATED C7H6 REARRANGEMENTS

Thermolysis or photolysis of phenyldiazomethane (2) produces phenylmethylene (3), which ring-expands to give 1,2,4,6-cycloheptatetraene (6).Spectroscopic and chemical evidence rule out bicyclo(4.1.0)hepta-2,4,6-triene (4), cycloheptatrienylidene (5), and bicyclo(3.2.0)hepta-1,3,6-triene (11) intermediates.The strained allene in cycloheptatetraene (6) exhibits infrared absorption at 1824 and 1816 cm-1.Deuterium substitution produces the expected 10-cm-1 shift in the allene absorption.Fluorine or chlorine substitution substantially enhances the allene absorption intensity.Deuterium labeling studies reveal that the intramolecular chemistry of cycloheptatetraene (6) involves reversible thermal or photochemical equilibriation with phenylmethylene (3).The intermolecular chemistry of 6 involves dimerization.At temperatures as low as 10 K, 6 forms a labile (2+2) dimer,7, which undergoes thermally allowed, electrocyclic ring opening to give heptafulvalene (8) upon warming to room temperature.The rearrangements of 7-acetoxynorbornadiene (9), 2-diazobicyclo(3.2.0)hepta-3,6-diene (31), and 8-diazobicyclo(2.2.2)octa-2,5-dien-7-one (33) all involve cycloheptatetraene (6) intermediates.

Chemiluminescence from arylcarbene oxidation: phenylchlorocarbene and (2-chlorophenyl)carbene

Chemiluminescence is observed in the thermal reaction of phenylchlorocarbene or (2-chloro-phenyl)carbene and O2, matrix-isolated in Ar.The chemiluminescence spectra closely match the phosphorescence of the corresponding carbonyl compounds.The reactivity of both carbenes towards O2 is very different.Singlet carbene phenylchlorocarbene reacts thermally only slowly with O2 up to 60 K.The oxidation products phenylchloroformate, benzoyl chloride and O(3P) are mainly formed photochemically on irradiation of the diazirine precursor.Triplet carbene (2-chlorophenyl)carbene reacts readily with O2 at cryogenic temperatures to give mostly 2-chlorobenzaldehyde-O-oxide.The carbonyl-O-oxide is photochemically easily cleaved to give 2-chlorobenzaldehyde and O(3P).The reaction step leading to carbonyl compounds in their excited states is in both carbene oxidations the recombination of the free carbene and O(3P).