311-75-1

Usage

InChI:InChI=1/C5H8/c1-4-2-5(1)3-4/h4-5H,1-3H2

Upstream product

• 98577-44-7 1,1-bis(chloromethyl)-2,2-dibromocyclopropane 
• 1165952-92-0 cyclohexa-1,4-diene 
• 71490-77-2 bicyclo<1.1.1>pent-1-yl radical 

Downstream Products

• 22287-32-7 1-Hydroxymethylbicyclo<1.1.1>pentane 
• 136399-10-5 1-iodo-3-methylbicyclo<1.1.1>pentane 
• 83249-04-1 3-phenylbicyclo<1.1.1>pentane-1-carboxylic acid 
• 156329-83-8 3-(p-methoxyphenyl)bicyclo<1.1.1>pentane-1-carboxylic acid 
• 102410-96-8 3,3'-diphenyl-1,1'-bi(bicyclo[1.1.1]pentane) 
• 245508-15-0 1,3-diphenylbicyclo[1.1.1]pentane 
• 83249-09-6 methyl 3-phenylbicyclo<1.1.1>pentane-1-carboxylate 
• 131515-52-1 methyl 3-(p-chlorophenyl)bicyclo<1.1.1>pentyl-1-carboxylate 
• 156329-80-5 3-(p-nitrophenyl)bicyclo<1.1.1>pentane-1-carboxylic acid 
• 159600-55-2 methyl 3-(p-nitrophenyl)bicyclo<1.1.1>pentyl-1-carboxylate 
• 105542-98-1 1,3-bisiodobicyclo[1.1.1]pentane 

Relevant academic research and scientific papers

Bicyclo[1.1.1]pent-1-yl: A tertiary alkyl radical with enhanced reactivity

Absolute rate constants for reactions of bicyclo[1.1.1]pent-1-yl radicals with α-methylstyrene (1.4 x 107 M-1s-1) and 1,4-cyclohexadiene (4.6 x 105 M-1s-1) at 25°C were measured by laser flash photolysis. This bridgehead radical is more reactive than tert-butyl which we attribute to its high s-character and the absence of steric shielding of the radical center.

γ-dissociations of 3-alkylbicyclo[1.1.1]pent-1-yl radicals into [1.1.1]propellane and alkyl radicals: Verification of a theoretical prediction

The γ-dissociations of 3-substituted bicyclo[1.1.1]pent-1-yl radicals and cyclobutyl radicals were investigated by ab initio SCF MO (HF, MP2, MP3 and MP4/6-31G*) and density functional methods (B3LYP/6-31G*). The transition states were found to resemble the product alkyl radical and [1.1.1]propellane or bicyclo[1.1.0]butane. Calculated endothermicities and energy barriers were comparatively low for loss of the t-butyl radical from the 3-t-butylbicyclo[1.1.1]pent-1-yl radical, which suggested that this dissociation would be significant under laboratory conditions. The dissociation was verified experimentally by means of the reaction of 1-iodo- 3-t-butylbicyclo[1.1.1]pentane with tributyltin hydride. Arrhenius parameters for this dissociation were determined by end product analysis. The SCF MO and density functional calculations resulted in much higher endothermicities and energy barriers for γ-dissociations of cyclobutyl radicals, hence neither the formation of bicyclo[1.1.0]butane nor alkyl radical addition to this bicyclic compound was predicted to be important.

Concerning the Synthesis of Propellane

The reaction of 1,1-dibromo-2,2-bis(chloromethyl)cyclopropane (2) with methyllithium in ether led to a solution of propellane (1) in a yield of 70percent. 1 could also be prepared free of solvent by reaction of 2 with lithium powder in triglyme/n-decane at 73 deg C. - Keywords: Cyclopropa annulation/ Propellane/ Polycycles, strained