14541-26-5

Upstream product

• 4222-25-7 3-bromo-3-phenyl-3H-diazirine 

Downstream Products

• 111888-03-0 (1S,2S)-3-Bromo-3-phenyl-1,2-bis-(2,4,6-tri-tert-butyl-phenyl)-diphosphirane 
• 618-32-6 Benzoyl bromide 
• 32047-17-9 1,2-dibromo-1,2-diphenylethylene 
• 4920-72-3 1-bromo-1-phenyl-2,2,3,3-tetramethylcyclopropane 
• 4920-73-4 1-bromo-1-phenyl-2,2,3-trimethylcyclopropane 
• 18963-53-6 ((S)-Bromo-methoxy-methyl)-benzene 

Relevant academic research and scientific papers

Volumes of Activation for the Cycloaddition Reactions of Phenylhalocarbenes to Alkenes

The absolute rate constants for the cycloaddition reactions of three arylhalocarbenes to two alkenes have been measured as a function of pressure in the range 0.1 to 203 MPa.In all cases the observed rate constants were found to increase with increasing pressure.The magnitude of the derived activation volumes falls in the range of -10 to -18 cm3/mol and does not depend on solvent.The results rule out a late, two-bond transition state and a bipolar single-bond transition state but are consistent with the reversible formation of a carbene-alkene complex or an early one- or two-bond transition state.

CHLOROACRYLONITRILE, A DETECTOR SUBSTRATE FOR CARBENE NUCLEOPHILICITY; APPLICATIONS TO PHENYLHALOCABENES

α-Chloroacrylonitrile is an excellent substrate for nucleophilic and ambiphilic carbenes; its use permits visualization of the latent ambiphilic properties of the phenylhalocarbenes.

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.

Spin selectivity in the oxygenation of singlet phenylhalocarbenes with oxygen

Singlet phenylhalocarbenes are shown to react with triplet oxygen and the apparent spin-forbidden oxygenation rates are strongly dependent on substituents, i.e. in the decreasing order of Br>Cl?F for halogen and of p-NO2>H?p-MeO for p-substituents. These results suggest the oxygenation of triplet halocarbene equilibrated with ground-state singlet, resulting in the first estimation of energy difference between the singlet and triplet states.

The Experimental Heats of Formation and Reaction of Singlet Carbenes via Time-Resolved Photoacoustic Calorimetry

The heats of formation and reaction of several singlet carbenes are determined by time-resolved photoacoustic calorimetry.The most selective and least reactive carbene examined, methoxychlorocarbene, is the most stable and reacts least exothermically with CH3OH.The phenylhalocarbenes have similar stabilities and reaction exothermicities with CH3OH.The experimental carbene heats of formation in solution are systematically lower and the stabilization energies higher than the values from MNDO calculations.This potentially result from (i) solvation of the carbene, (ii) an unresolved reaction volume change, or (iii) incorrect MNDO calculated carbene and diaziridine enthalpies.

ABSOLUTE RATE CONSTANTS FOR THE ADDITIONS OF HALOPHENYLCARBENES TO ALKENES; A REACTIVITY-SELECTIVITY RELATION

The absolute rate constants determined for the additions of FCPh, ClCPh, and BrCPh to Me2C=CMe2, Me2C=CHMe, trans-MeCH=CHEt, and n-BuCH=CH2, appear to follow a reactivity/selectivity pattern of the "normal" (inverse) type.