96929-65-6

Upstream product

• 768-90-1 1-Adamantyl bromide 
• 263903-47-5 (3-noradamantyl)diazirine 

Relevant academic research and scientific papers

Rearrangement of 1-noradamantyl and 1-adamantylcarbene to bridgehead alkenes: Lifetimes of two bridgehead carbenes in solution

B3LYP density functional calculations with the 6-31G* basis set predict that 3-noradamantylcarbene 7 rearranges to adamantene 9 and protoadmant-3-ene 10 over barriers of 0.35 and 7.84 kcal/mol, respectively, after zero-point energy correction. The same level of theory predicts that 1-adamantylcarbene 8 rearranges to homoadamantene 11 over a barrier of 6.06 kcal/mol after zero-point energy correction. To test these predictions, the photochemistry of 3-noradamantyldiazirine 5 and 1-adamantyldiazirine 6 was studied. Photolysis of 5 and 6 in cyclohexane produces the known dimers of the strained alkenes. 1-Adamantylcarbene 8 can be trapped in solution with cyclohexane and piperidine. 1-Adamantylcarbene 8 can be trapped with pyridine to form an ylide upon laser flash photolysis (LFP) of 6. 3-Noradamantylcarbene 7 cannot be intercepted with pyridine in LFP experiments. 3-Noradamantylcarbene 7 is not trapped with cyclohexane and is trapped with piperidine in only miniscule yield. The data indicates that 1-adamantylcarbene 8 is formed more efficiently from its diazirine precursor than is 3-noradamantylcarbene 7 and that the solution-phase lifetime of 1-adamantylcarbene 8 is at least 10 times longer than that of 3-noradamantylcarbene 7.

REACTION OF 1-BROMOADAMANTANE WITH AN ALCOHOL SOLUTION OF ALKALI

The main direction in the reaction of 1-bromotricyclo3,7>decane with an alcohol solution of potassium hydroxide is solvolysis with the formation of tricyclo3,7>decan-1-ol and tricyclo3,8>decan-3-ol.Dehydrobromination takes place to a lesser degree, leading to tetracyclo3,7.02,4>decane and tricyclo3,8>dec-4-ene.